Phase change inks

ABSTRACT

Phase change inks comprising a phase change ink carrier and a colorant compound of the formula  
                 
 
wherein R 1 , R 2 , R 3 , R 4 , R 5 , m, n, and p are as defined herein, R 6  is a direct bond, an alkylene group, an arylene group, an arylalkylene group, or an alkylarylene group, R 66  is an alkylene group, an arylene group, an arylalkylene group, or an alkylarylene group, G is a hydroxy group, a carboxylic acid group, an alkyl group having at least about 8 carbon atoms, an aryl group, an arylalkyl group having at least about 14 carbon atoms, an alkylaryl group having at least about 14 carbon atoms, a group of the formula  
                 
 
a group of the formula  
                 
 
a group of the formula  
                 
 
or a group of the formula  
                 
 
X is —O— or —NR 9 —, and R 7 , R 8 , and R 9  are as defined herein.

CROSS-REFERENCE TO RELATED APPLICATIONS

Copending application U.S. Ser. No. 10/260,146, filed Sep. 27, 2002,entitled “Colorant Compounds,” U.S. Publication 20040077887, with thenamed inventors Jeffery H. Banning and C. Wayne Jaeger, the disclosureof which is totally incorporated herein by reference, disclosescompounds of the formula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group or an arylalkylene group, and X is(a) a hydrogen atom, (b) a group of the formula

wherein R₂ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, (c) an alkyleneoxy, aryleneoxy, arylalkyleneoxy, oralkylaryleneoxy group, or (d) a group of the formula

wherein R₄ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group.

Copending application U.S. Ser. No. 10/260,376, filed Sep. 27, 2002,U.S. Publication 20040102540, entitled “Phase Change Inks,” with thenamed inventors C. Wayne Jaeger and Jeffery H. Banning, the disclosureof which is totally incorporated herein by reference, discloses a phasechange ink composition comprising a phase change ink carrier and acolorant compound of the formula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group or an arylalkylene group, and X is(a) a hydrogen atom, (b) a group of the formula

wherein R₂ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, (c) an alkyleneoxy, aryleneoxy, arylalkyleneoxy, oralkylaryleneoxy group, or (d) a group of the formula

wherein R₄ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group.

Copending application U.S. Ser. No. 10/260,379, filed Sep. 27, 2002,U.S. Publication 20040082801, entitled “Methods for Making ColorantCompounds,” with the named inventors C. Wayne Jaeger and Jeffery H.Banning, the disclosure of which is totally incorporated herein byreference, discloses a process for preparing a colorant of the formula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group or an arylalkylene group, R₂ is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and R₄ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, can be prepared by a process which comprises (a)preparing a first reaction mixture by admixing (1) leucoquinizarin and,optionally, quinizarin, (2) an aminobenzene substituted with an alcoholgroup of the formula —R₁—OH, (3) boric acid, and (4) an optionalsolvent, and heating the first reaction mixture to prepare analcohol-substituted colorant of the formula

followed by (b) converting the colorant thus prepared to either (i) anester-substituted colorant by reaction with an esterification compoundwhich is either (A) an anhydride of the formula

or (B) an acid of the formula R₂COOH in the presence of an optionalesterification catalyst, or (ii) a urethane-substituted colorant byreaction with an isocyanate compound of the formulaR₄—N═C═Oand (c) brominating the colorant thus prepared, wherein eitherconversion to ester or urethane can be performed before bromination orbromination can be performed before conversion to ester or urethane.

Copending application U.S. Ser. No. ______ (not yet assigned; AttorneyDocket No. A3384-US-NP), filed Jul. 29, 2004, entitled “ColorantCompounds,” with the named inventors Jeffery H. Banning, Wolfgang G.Wedler, and C. Wayne Jaeger, the disclosure of which is totallyincorporated herein by reference, discloses a colorant compound of theformula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group, an arylene group, an arylalkylenegroup, or an alkylarylene group, provided that no oxygen atom creates a

linkage, X is —O— or —NR₃— wherein R₃ is a hydrogen atom, an alkylgroup, an aryl group, an arylalkyl group, or an alkylaryl group, and R₂is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group.

Copending application U.S. Ser. No. ______ (not yet assigned; AttorneyDocket No. A3384Q-US-NP), filed Jul. 29, 2004, entitled “Phase ChangeInks,” with the named inventors Jeffery H. Banning, Wolfgang G. Wedler,and C. Wayne Jaeger, the disclosure of which is totally incorporatedherein by reference, discloses a phase change ink composition comprisinga phase change ink carrier and a colorant compound of the formula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group, an arylene group, an arylalkylenegroup, or an alkylarylene group, provided that no oxygen atom creates a

linkage, X is —O— or —NR₃— wherein R₃ is a hydrogen atom, an alkylgroup, an aryl group, an arylalkyl group, or an alkylaryl group, and R₂is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group.

Copending application U.S. Ser. No. ______ (not yet assigned; AttorneyDocket No. A3383-US-NP), filed concurrently herewith, entitled “ColorantCompounds,” with the named inventors Jeffery H. Banning, Wolfgang G.Wedler, and C. Wayne Jaeger, the disclosure of which is totallyincorporated herein by reference, discloses compounds of the formula

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₆₆, m, n, p, and G are as definedtherein.

BACKGROUND

Disclosed herein are phase change inks. More specifically, disclosedherein are hot melt or phase change inks containing specific colorantcompounds. One embodiment is directed to a phase change ink compositioncomprising a phase change ink carrier and a colorant compound of theformula

wherein R₁ is (i) a hydrogen atom, (ii) an alkyl group, (iii) an arylgroup, (iv) an arylalkyl group, or (v) an alkylaryl group, R₂ is (i) ahydrogen atom, (ii) an alkyl group, (iii) an aryl group, (iv) anarylalkyl group, (v) an alkylaryl group, or (vi) a substituent otherthan an alkyl, aryl, arylalkyl, or alkylaryl group, R₃ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, m is an integer of 0, 1, 2, 3, or 4, R₄ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, n is an integer of 0, 1, 2, 3, or 4, R₅ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, p is an integer of 0, 1, 2, 3, or 4, R₆ is (i) a directbond, (ii) an alkylene group, (iii) an arylene group, (iv) anarylalkylene group, or (v) an alkylarylene group, R₆₆ is (i) an alkylenegroup, (ii) an arylene group, (iii) an arylalkylene group, or (iv) analkylarylene group, G is (1) a hydroxy group, (2) a carboxylic acidgroup, (3) an alkyl group having at least about 8 carbon atoms, (4) anaryl group, (5) an arylalkyl group having at least about 14 carbonatoms, (6) an alkylaryl group having at least about 14 carbon atoms, (7)a group of the formula

(8) a group of the formula

(9) a group of the formula

or (10) a group of the formula

R₇ is (i) an alkyl group, (ii) an aryl group, (iii) an arylalkyl group,or (iv) an alkylaryl group, R₈ is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup, X is —O— or —NR₉—, and R₉ is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup.

In general, phase change inks (sometimes referred to as “hot melt inks”)are in the solid phase at ambient temperature, but exist in the liquidphase at the elevated operating temperature of an ink jet printingdevice. At the jet operating temperature, droplets of liquid ink areejected from the printing device and, when the ink droplets contact thesurface of the recording substrate, either directly or via anintermediate heated transfer belt or drum, they quickly solidify to forma predetermined pattern of solidified ink drops. Phase change inks havealso been used in other printing technologies, such as gravure printing,as disclosed in, for example, U.S. Pat. No. 5,496,879 and German PatentPublications DE 4205636AL and DE 4205713AL, the disclosures of each ofwhich are totally incorporated herein by reference.

Phase change inks for color printing typically comprise a phase changeink carrier composition which is combined with a phase change inkcompatible colorant. In a specific embodiment, a series of colored phasechange inks can be formed by combining ink carrier compositions withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks can comprise four component dyes, namely,cyan, magenta, yellow and black, although the inks are not limited tothese four colors. These subtractive primary colored inks can be formedby using a single dye or a mixture of dyes. For example, magenta can beobtained by using a mixture of Solvent Red Dyes or a composite black canbe obtained by mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat.No. 4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each ofwhich are totally incorporated herein by reference, teach that thesubtractive primary colorants employed can comprise dyes from theclasses of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acidand Direct Dyes, and Basic Dyes. The colorants can also includepigments, as disclosed in, for example, U.S. Pat. No. 5,221,335, thedisclosure of which is totally incorporated herein by reference. U.S.Pat. No. 5,621,022, the disclosure of which is totally incorporatedherein by reference, discloses the use of a specific class of polymericdyes in phase change ink compositions.

Phase change inks have also been used for applications such as postalmarking, industrial marking, and labelling.

Phase change inks are desirable for ink jet printers because they remainin a solid phase at room temperature during shipping, long term storage,and the like. In addition, the problems associated with nozzle cloggingas a result of ink evaporation with liquid ink jet inks are largelyeliminated, thereby improving the reliability of the ink jet printing.Further, in phase change ink jet printers wherein the ink droplets areapplied directly onto the final recording substrate (for example, paper,transparency material, and the like), the droplets solidify immediatelyupon contact with the substrate, so that migration of ink along theprinting medium is prevented and dot quality is improved.

Compositions suitable for use as phase change ink carrier compositionsare known. Some representative examples of references disclosing suchmaterials include U.S. Pat. No. 3,653,932, U.S. Pat. No. 4,390,369, U.S.Pat. No. 4,484,948, U.S. Pat. No. 4,684,956, U.S. Pat. No. 4,851,045,U.S. Pat. No. 4,889,560, U.S. Pat. No. 5,006,170, U.S. Pat. No.5,151,120, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,496,879, EuropeanPatent Publication 0187352, European Patent Publication 0206286, GermanPatent Publication DE 4205636AL, German Patent Publication DE 4205713AL,and PCT Patent Application WO 94/04619, the disclosures of each of whichare totally incorporated herein by reference. Suitable carrier materialscan include paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters, for example), andmany synthetic resins, oligomers, polymers, and copolymers.

U.S. Pat. No. 6,395,078 (Jaeger), U.S. Pat. No. 6,422,695 (Jaeger),Canadian Patent Publication 2 355 533 (filed Aug. 20, 2001, publishedFeb. 23, 2002), European Patent Publication EP 1 182 232 (filed Aug. 17,2001, published Feb. 27, 2001), Japanese Patent Publication JP2002129044 (filed Aug. 8, 2001, published May 9, 2002), Brazilian PatentPublication PI01035819 (filed Aug. 22, 2001, published Mar. 26, 2002),and Mexican Patent Application 2001008418 (filed Aug. 20, 2001), thedisclosures of each of which are totally incorporated herein byreference, disclose a compound having the formula

wherein at least one Q₁, Q₂, Q₃, and Q₄ is a halogen atom and any of Q₁,Q₂, Q₃ and Q₄ which is not a halogen atom is a hydrogen atom; andwherein R comprises at least two carbon atoms. The invention furtherencompasses inclusion of such compound into phase change ink carriercompositions, as well as printing methods utilizing such compound.

British Patent Publication GB 2 021 138 (Hohmann et al.), the disclosureof which is totally incorporated herein by reference, discloses mixturesof dyestuffs of the formula

and of the formula

wherein R₁, R₂, and R₃ denote C₁-C₄ alkyl, C₁-C₄ alkoxy, or halogen, andn denotes 2 or 3, which are suitable for dyeing polyester fibers by theexhaustion process. Dark blue and navy blue dyeings with good fastnessproperties are obtained.

U.S. Pat. No. 6,174,937 (Banning et al.), the disclosure of which istotally incorporated herein by reference, discloses a phase change inkcomprising a material of the formula

wherein X₁, X₂, X₃ and X₄ are segments comprising atoms selected fromgroups V and VI of the periodic table; wherein at least one R₁ and R₅comprises at least 37 carbon units; and wherein R₂, R₃ and R₄ eachcomprise at least one carbon unit. The invention further encompasses acomposition of matter, as well as methods of reducing coefficients offriction of phase change ink formulations.

U.S. Pat. No. 5,507,864 (Jaeger et al.), the disclosure of which istotally incorporated herein by reference, discloses a phase change inkcomposition that includes a combination of different dye types such asan anthraquinone dye and a xanthene dye, which is most preferably arhodamine dye. While each dye type is insufficiently soluble withrespect to favored carrier compositions to preserve color saturation inreduced ink quantity prints, the dye type combination permits increaseddye loading and maintains print quality. In a preferred embodiment ofthe invention, a favored carrier composition is adjusted to promote thecolored form of a preferred rhodamine dye (C.I. Solvent Red 49) andmixed with a preferred anthraquinone dye (C.I. Solvent Red 172) whoseconcentration is kept below a critical level to prevent post printedblooming. The resulting preferred phase change ink compositions providea magenta phase change ink with enhanced light fastness and colorsaturation, as well as good compatibility with preferred existingsubtractive primary color phase change inks.

U.S. Pat. No. 5,902,841 (Jaeger et al.), the disclosure of which istotally incorporated herein by reference, discloses a phase change inkcomposition wherein the ink composition utilizes a colorant incombination with a selected phase change ink carrier compositioncontaining at least one hydroxy-functional fatty amide compound.

R. Butnaru et al.; “Researches on Dyeing of Cotton Fabrics with AcidDyestuffs, Concomitantly with Crease-Resist Treatments,” Cellulose Chem.Technol., 29, p. 471 (1995), the disclosure of which is totallyincorporated herein by reference, discloses an analysis of the resultsobtained on dyeing of cotton cellulosic fabrics with acid dyestuffs, onemploying crease-resist agents with polyfunctional structure. Theconclusion was reached that no chemical or physical bonds occur betweendyestuffs and the fiber, the dyestuffs being fixed onto the resin'saminic groups formed as a result of the thermal, crease-resisttreatment. Washing resistance of the cellulosic materials thus dyedattained the values obtained as a result of dyeing with directdyestuffs, specific for these types of fibers.

U.S. Pat. No. 6,235,094 (Banning et al.), the disclosure of which istotally incorporated herein by reference, discloses a compound havingthe formula

wherein R₁, Z and the carbonyl can be comprised by a common ring,wherein R₁ comprises a chromophore that absorbs light from the visiblewavelength range, and wherein n is an integer that is at least 12. Theinvention also encompasses a solid phase change ink composition. Suchcomposition includes a phase change ink carrier and a colorant. Thecolorant comprises a chromophore that absorbs light from the visiblewavelength range, and has the formula

wherein R₁, Z and the carbonyl can be comprised by a common ring,wherein n is an integer that is at least 12. Additionally, the inventionencompasses a method of forming a colorant. A first compound having theformula

is reacted with a second compound having the formula Z(CH₂)_(n)CH₃,wherein n is an integer that is at least 12, to form a third compoundhaving the formula

wherein the third compound comprises a chromophore that absorbs lightfrom the visible wavelength range.

U.S. Pat. No. 3,734,934 (Kolliker et al.), the disclosure of which istotally incorporated herein by reference, discloses dyestuffs of theformula

wherein W is chlorine, bromine, cyano, lower alkyl, lower alkoxy,carbonyl, phenoxycarbonyl, lower alkylthio, phenylthio, lower alkylsulfonyl, or a grouping of the formula

wherein Z is —CO— or —SO₂— and R₁ and R₂ are each independently hydrogenor lower alkyl, Y is lower alkylene, —CH₂CH₂OCH₂CH₂—, or—CH₂CH₂CH₂OCH₂CH₂CH₂—, X is a direct bond, —O—, —S—, —NH—, —COHN—, or—SO₂NH—, R″ is lower alkyl, cyclohexyl, phenyl, or phenyl substituted bychlorine, lower alkyl, or lower alkoxy, or bromine, the nucleus B iseither unsubstituted or further monosubstituted by chlorine, loweralkyl, or lower alkoxy, E is NH₂, OH, or NHT, and T is lower alkyl,cyclohexyl, phenyl, lower alkyl phenyl, or phenoxyphenyl.

British Patent 687,807, the disclosure of which is totally incorporatedherein by reference, discloses hydroxyethoxymethylphenyl-amino-anthraquinone dyestuffs and derivatives thereof of theformula

wherein X is hydrogen or methyl, R is hydrogen or CH₃OCH₂CH₂OZ, Z ishydrogen, hydroxy alkyl, or alkoxy alkyl, and Y is hydrogen, hydroxy, or

These compounds exhibit substantially enhanced substantivity for acetaterayon and have the ability to withstand the action of acid gas fumessuch as the combustion products of industrial and engine fuels.

Japanese Patent Publication 63223064, the disclosure of which is totallyincorporated herein by reference, discloses a blue coloring material foruse in optical filters which is of the formula

wherein R₁ to R₃ are each H, alkyl, alkoxy alkyl, hydroxy alkyl, orhalogen, R₄ is acyl, (alkyl)carbamoyl, arylcarbamoyl, aralkylcarbamoyl,alkenylcarbamoyl, methanesulfonyl, or H, X is alkylene,alkylene-O-alkylene, or alkylene-S-alkylene, and n is 1 or 2. An exampleis 1-{4-(2-benzoyloxyethyl)anilino}-4-hydroxyanthraquinone.

“British Intelligence Objectives Subcommittee Report 1484”, PublicationBoard No. 86139, Library of Congress, Washington, D.C., 1947, p. 46-47,the disclosure of which is totally incorporated by reference, disclosesthe synthesis of 4-bromo-1:9-N-methylanthrapyridone and similarcompounds.

U.S. Pat. No. 6,152,969 (Matsumoto et al.), the disclosure of which istotally incorporated herein by reference, discloses a coloring matterwhich has a moderately bluish magenta color and an excellentlightfastness and can provide a wide range of color tones in the visiblerange when used together with yellow and cyan inks. A water-base inkcomposition or the like is prepared by using a sulfonic acid derivativeof an anthrapyridone compound represented by general formula

as a magenta dye, wherein R₁′ represents alkoxycarbonyl, carbonyl, orbenzoyl; R₂ represents hydrogen or alkyl; and R₃ and R₄ represent eachindependently hydrogen, halogeno, alkyl, or alkoxy.

U.S. Pat. No. 5,340,910 (Chamberlin et al.), the disclosure of which istotally incorporated herein by reference, discloses an improved processfor the synthesis of 1-cyano-3H-dibenz(f,ij) isoquinoline-2,7-dionecompounds, and a process exhibiting improvements in quality of products,safety, fewer environmental concerns, and economics when compared topresently known processes. The compounds are useful as colorants forpolyesters and selected compounds, and when combined with smallquantities of certain red colorants are particularly efficacious as bluetoners for polyesters.

U.S. Pat. No. 4,386,206 (Wingard, Jr. et al.), the disclosure of whichis totally incorporated herein by reference, discloses anthrapyridonesprepared in high yields from 1-aminoanthraquinones or1-alkylaminoanthraquinones and phenylacetyl halides when tertiary amidesare employed as reaction media. The phenylacetyl halides can begenerated in situ from phenylacetic acid and thionyl halide or phosgene.

U.S. Pat. No. 2,644,821 (Peter et al.), the disclosure of which istotally incorporated herein by reference, discloses anthrapyridonedyestuffs of the general formula

wherein X stands for phenyl or alkylphenyl and Y stands for phenyl ortetrahydronaphthyl, either of which may carry any desired substituent orsubstituents other than solubilizing groups, such as sulfonic acid orcarboxylic acid groups, and R represents hydrogen, methyl, Cl, Br,methoxy, or nitro.

U.S. Pat. No. 4,745,174 (Pruett et al.), the disclosure of which istotally incorporated herein by reference, discloses fiber formingpolyester compositions that exhibit improved whiteness by incorporatingderivatives of dibenzoisoquinolinediones of the formula

wherein R is hydrogen, cycloalkyl, allyl, alkyl, aralkyl, alkoxyalkyl,or cycloalkylalkylene; R₁ is hydrogen, halogen, alkyl, alkoxy, aryloxy,alkylthio, or arylthio; R₂ is hydrogen, halogen, alkyl, aryl, alkoxy,aryloxy, alkylthio, arylthio, carbalkoxy, carbaryloxy, carbaralkyloxy,carboxy, sulfamoyl, alkylsulfamoyl, dialkylsulfamoyl,alkylarylsulfamoyl, cycloalkylsulfamoyl, arylsulfamoyl, carbamoyl,alkylcarbamoyl, dialkylcarbamoyl, alkylarylcarbamoyl,cycloalkylcarbamoyl, arylcarbamoyl, 2-pyrrolidono, acylamido, orN-alkylacylamido; R₃ is one or more groups selected from the groupconsisting of hydrogen, halogen, alkyl, and alkoxy; and x is an integerof 1 to 5; wherein one or more alkyl, alkoxy, aryl, aryloxy, alkylthio,arylthio or aralkyl residues may contain one or more reactive groupsselected from the group consisting of carboxy, carbalkoxy, carbaryloxy,N-alkyl-carbamoyloxy, carbamoyloxy, acyloxy, chlorocarbonyl, hydroxyl,cycloalkylcarbonyloxy, N-arylcarbamoyloxy, and N,N-dialkylcarbamoyloxy,wherein said alkyl and aryl groups may also have common substituentssuch as alkoxy, acyloxy, cyano, halogen, hydroxy, and acylamido.

While known compositions and processes are suitable for their intendedpurposes, a need remains for improved colorant compounds. In addition, aneed remains for colorant compositions particularly suitable for use inphase change inks. Further, a need remains for colorant compounds with adesirable magenta color. Additionally, a need remains for colorantcompounds with desirable thermal stability. There is also a need forcolorant compounds with good lightfastness. In addition, there is a needfor colorant compounds that exhibit desirable solubility characteristicsin phase change ink carrier compositions. Further, there is a need forcolorant compounds that, when incorporated into phase change inks,exhibit reduced migration within a layer of printed ink. Additionally,there is a need for colorant compounds that, when incorporated intophase change inks, exhibit reduced crystallization within a layer ofprinted ink. A need also remains for colorant compounds that, whenincorporated into phase change inks, enable production of prints thatmaintain uniform color over long periods of time without unevenness orblotching. In addition, a need remains for colorant compounds that, whenincorporated into phase change inks, enable production of prints thatretain their original color over long periods of time. Further, a needremains for colorant compounds that, when incorporated into phase changeinks, enable production of prints that exhibit reduced sensitivity toimage discoloration upon contact with human fingertips. Additionally, aneed remains for colorant compounds that can be incorporated into phasechange inks in desirably high concentrations. There is also a need forcolorant compounds that can be manufactured easily and practically.

SUMMARY

Disclosed herein are phase change ink compositions comprising a phasechange ink carrier and a colorant compound of the formula

wherein R₁ is (i) a hydrogen atom, (ii) an alkyl group, (iii) an arylgroup, (iv) an arylalkyl group, or (v) an alkylaryl group, R₂ is (i) ahydrogen atom, (ii) an alkyl group, (iii) an aryl group, (iv) anarylalkyl group, (v) an alkylaryl group, or (vi) a substituent otherthan an alkyl, aryl, arylalkyl, or alkylaryl group, R₃ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, m is an integer of 0, 1, 2, 3, or 4, R₄ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, n is an integer of 0, 1, 2, 3, or 4, R₅ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, p is an integer of 0, 1, 2, 3, or 4, R₆ is (i) a directbond, (ii) an alkylene group, (iii) an arylene group, (iv) anarylalkylene group, or (v) an alkylarylene group, R₆₆ is (i) an alkylenegroup, (ii) an arylene group, (iii) an arylalkylene group, or (iv) analkylarylene group, G is (1) a hydroxy group, (2) a carboxylic acidgroup, (3) an alkyl group having at least about 8 carbon atoms, (4) anaryl group, (5) an arylalkyl group having at least about 14 carbonatoms, (6) an alkylaryl group having at least about 14 carbon atoms, (7)a group of the formula

(8) a group of the formula

(9) a group of the formula

or (10) a group of the formula

R₇ is (i) an alkyl group, (ii) an aryl group, (iii) an arylalkyl group,or (iv) an alkylaryl group, R₈ is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup, X is —O— or —NR₉—, and R₉ is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup.

DETAILED DESCRIPTION

The phase change ink compositions disclosed herein contain colorantcompounds of the formula

wherein R₁ is (i) a hydrogen atom, (ii) an alkyl group (includinglinear, branched, saturated, unsaturated, cyclic, substituted, andunsubstituted alkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the alkyl group), in one embodiment with at leastabout 1 carbon atom, and in one embodiment with no more than about 50carbon atoms, in another embodiment with no more than about 18 carbonatoms, and in yet another embodiment with no more than about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges, (iii) an aryl group (including substituted and unsubstitutedaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least about 5 carbon atoms,and in another embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (iv) an arylalkyl group(including substituted and unsubstituted arylalkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either the aryl or thealkyl portion of the arylalkyl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms,and in yet another embodiment with no more than about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, or (v) an alkylaryl group (including substitutedand unsubstituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either the alkyl or the aryl portion of thealkylaryl group), in one embodiment with at least about 6 carbon atoms,and in another embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as tolyl or thelike, with specific examples of R₁ groups including (but not beinglimited to) a hydrogen atom, a methyl group, and the like, R₂ is (i) ahydrogen atom, (ii) an alkyl group (including linear, branched,saturated, unsaturated, cyclic, substituted, and unsubstituted alkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkyl group), in one embodiment with at least about 1 carbon atom,and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 18 carbon atoms, and in yetanother embodiment with no more than about 12 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (iii) an arylgroup (including substituted and unsubstituted aryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the aryl group), in oneembodiment with at least about 5 carbon atoms, and in another embodimentwith at least about 6 carbon atoms, and in one embodiment with no morethan about 50 carbon atoms, in another embodiment with no more thanabout 18 carbon atoms, and in yet another embodiment with no more thanabout 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (iv) an arylalkyl group (including substitutedand unsubstituted arylalkyl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either the aryl or the alkyl portion of thearylalkyl group), in one embodiment with at least about 6 carbon atoms,and in another embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as benzyl or thelike, (v) an alkylaryl group (including substituted and unsubstitutedalkylaryl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in either the alkyl or the aryl portion of the alkylaryl group),in one embodiment with at least about 6 carbon atoms, and in anotherembodiment with at least about 7 carbon atoms, and in one embodimentwith no more than about 50 carbon atoms, in another embodiment with nomore than about 18 carbon atoms, and in yet another embodiment with nomore than about 12 carbon atoms, although the number of carbon atoms canbe outside of these ranges, such as tolyl or the like, or (vi) asubstituent other than an alkyl, aryl, arylalkyl, or alkylaryl group,including (but not limited to) hydroxy groups, halogen atoms, aminegroups, imine groups, ammonium groups, cyano groups, pyridine groups,pyridinium groups, ether groups, aldehyde groups, ketone groups, estergroups, amide groups, carbonyl groups, thiocarbonyl groups, sulfategroups, sulfonate groups, sulfonic acid groups, sulfide groups,sulfoxide groups, phosphine groups, phosphonium groups, phosphategroups, nitrile groups, mercapto groups, nitro groups, nitroso groups,sulfone groups, acyl groups, acid anhydride groups, azide groups, azogroups, cyanato groups, isocyanato groups, thiocyanato groups,isothiocyanato groups, carboxylate groups, carboxylic acid groups,urethane groups, urea groups, mixtures thereof, and the like, whereintwo or more substituents can be joined together to form a ring, withsome specific examples of R₂ groups including (but not being limited to)—H, —CN, a phenyl group (—C₆H₅), an ester group of the formula—C(═O)OR₈₈ wherein R₈₈ is an alkyl group, such as methyl, ethyl, propyl,or the like, and the like, R₃ is (i) an alkyl group (including linear,branched, saturated, unsaturated, cyclic, substituted, and unsubstitutedalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in the alkyl group), in one embodiment with at least about 1carbon atom, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms,and in yet another embodiment with no more than about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, (ii)an aryl group (including substituted and unsubstituted aryl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the arylgroup), in one embodiment with at least about 5 carbon atoms, and inanother embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (iii) an arylalkyl group(including substituted and unsubstituted arylalkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either the aryl or thealkyl portion of the arylalkyl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms,and in yet another embodiment with no more than about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, (iv) an alkylaryl group (including substitutedand unsubstituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either the alkyl or the aryl portion of thealkylaryl group), in one embodiment with at least about 6 carbon atoms,and in another embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as tolyl or thelike, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, including (but not limited to) hydroxy groups, halogenatoms, amine groups, imine groups, ammonium groups, cyano groups,pyridine groups, pyridinium groups, ether groups, aldehyde groups,ketone groups, ester groups, amide groups, carbonyl groups, thiocarbonylgroups, sulfate groups, sulfonate groups, sulfonic acid groups, sulfidegroups, sulfoxide groups, phosphine groups, phosphonium groups,phosphate groups, nitrile groups, mercapto groups, nitro groups, nitrosogroups, sulfone groups, acyl groups, acid anhydride groups, azidegroups, azo groups, cyanato groups, isocyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring,m is an integer of 0, 1, 2, 3, or 4, R₄ is (i) an alkyl group (includinglinear, branched, saturated, unsaturated, cyclic, substituted, andunsubstituted alkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the alkyl group), in one embodiment with at leastabout 1 carbon atom, and in one embodiment with no more than about 50carbon atoms, in another embodiment with no more than about 18 carbonatoms, and in yet another embodiment with no more than about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges, (ii) an aryl group (including substituted and unsubstituted arylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least about 5 carbon atoms,and in another embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (iii) an arylalkyl group(including substituted and unsubstituted arylalkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either the aryl or thealkyl portion of the arylalkyl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms,and in yet another embodiment with no more than about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, (iv) an alkylaryl group (including substitutedand unsubstituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either the alkyl or the aryl portion of thealkylaryl group), in one embodiment with at least about 6 carbon atoms,and in another embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as tolyl or thelike, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, including (but not limited to) hydroxy groups, halogenatoms, amine groups, imine groups, ammonium groups, cyano groups,pyridine groups, pyridinium groups, ether groups, aldehyde groups,ketone groups, ester groups, amide groups, carbonyl groups, thiocarbonylgroups, sulfate groups, sulfonate groups, sulfonic acid groups, sulfidegroups, sulfoxide groups, phosphine groups, phosphonium groups,phosphate groups, nitrite groups, mercapto groups, nitro groups, nitrosogroups, sulfone groups, acyl groups, acid anhydride groups, azidegroups, azo groups, cyanato groups, isocyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring,n is an integer of 0, 1, 2, 3, or 4, R₅ is (i) an alkyl group (includinglinear, branched, saturated, unsaturated, cyclic, substituted, andunsubstituted alkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the alkyl group), in one embodiment with at leastabout 1 carbon atom, and in one embodiment with no more than about 50carbon atoms, in another embodiment with no more than about 18 carbonatoms, and in yet another embodiment with no more than about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges, (ii) an aryl group (including substituted and unsubstituted arylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least about 5 carbon atoms,and in another embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (iii) an arylalkyl group(including substituted and unsubstituted arylalkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either the aryl or thealkyl portion of the arylalkyl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms,and in yet another embodiment with no more than about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, (iv) an alkylaryl group (including substitutedand unsubstituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either the alkyl or the aryl portion of thealkylaryl group), in one embodiment with at least about 6 carbon atoms,and in another embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as tolyl or thelike, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, including (but not limited to) hydroxy groups, halogenatoms, amine groups, imine groups, ammonium groups, cyano groups,pyridine groups, pyridinium groups, ether groups, aldehyde groups,ketone groups, ester groups, amide groups, carbonyl groups, thiocarbonylgroups, sulfate groups, sulfonate groups, sulfonic acid groups, sulfidegroups, sulfoxide groups, phosphine groups, phosphonium groups,phosphate groups, nitrile groups, mercapto groups, nitro groups, nitrosogroups, sulfone groups, acyl groups, acid anhydride groups, azidegroups, azo groups, cyanato groups, isocyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring,p is an integer of 0, 1, 2, 3, or 4, R₆ is (i) a direct bond (i.e., R₆can be missing entirely and the G group can be directly bonded to thearomatic ring), (ii) an alkylene group (including linear, branched,saturated, unsaturated, cyclic, substituted, and unsubstituted alkylenegroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkylene group), in one embodiment with at least about 1 carbonatom, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 18 carbon atoms, in yetanother embodiment with no more than about 12 carbon atoms, in stillanother embodiment with no more than about 2 carbon atoms, and inanother embodiment with exactly 1 carbon atom, although the number ofcarbon atoms can be outside of these ranges, (iii) an arylene group(including unsubstituted and substituted arylene groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the arylene group), in oneembodiment with at least about 5 carbon atoms, and in another embodimentwith at least about 6 carbon atoms, and in one embodiment with no morethan about 50 carbon atoms, in another embodiment with no more thanabout 18 carbon atoms, in yet another embodiment with no more than about12 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, (iv) an arylalkylene group (including unsubstituted andsubstituted arylalkylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the aryl and the alkylportions of the arylalkylene group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms, inyet another embodiment with no more than about 12 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, such asbenzyl or the like, including (a) arylalkylene groups wherein both thearyl and the alkyl portions form the linkage between the

moiety and the-Gmoiety, such as

and the like, and (b) arylalkylene groups wherein only the alkyl portionforms the linkage between the

moiety and the-Gmoiety and the alkyl portion has aryl portions pending therefrom, suchas

and the like, or (v) an alkylarylene group (including unsubstituted andsubstituted alkylarylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the aryl and the alkylportions of the alkylarylene group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms, inyet another embodiment with no more than about 12 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, such astolyl, phenylethyl, or the like, including (a) alkylarylene groupswherein both the aryl and the alkyl portions form the linkage betweenthe

moiety and the-Gmoiety, such as

and the like, and (b) alkylarylene groups wherein only the aryl portionforms the linkage between the

moiety and the-Gmoiety and the aryl portion has alkyl portions pending therefrom, suchas

and the like, with specific examples of R₆ including (but not beinglimited to) —CH₂—, —CH₂CH₂—, and the like, R₆₆ is (i) an alkylene group(including linear, branched, saturated, unsaturated, cyclic,substituted, and unsubstituted alkylene groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the alkylene group), in oneembodiment with at least about 1 carbon atom, and in one embodiment withno more than about 50 carbon atoms, in another embodiment with no morethan about 18 carbon atoms, in yet another embodiment with no more thanabout 12 carbon atoms, in still another embodiment with no more thanabout 2 carbon atoms, and in another embodiment with exactly 1 carbonatom, although the number of carbon atoms can be outside of theseranges, (ii) an arylene group (including unsubstituted and substitutedarylene groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in the arylene group), in one embodiment with at least about 5carbon atoms, and in another embodiment with at least about 6 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 18 carbon atoms, in yetanother embodiment with no more than about 12 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (iii) anarylalkylene group (including unsubstituted and substituted arylalkylenegroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither or both of the aryl and the alkyl portions of the arylalkylenegroup), in one embodiment with at least about 6 carbon atoms, and inanother embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as benzyl or thelike, including (a) arylalkylene groups wherein both the aryl and thealkyl portions form the linkage between the

moiety and the-Gmoiety, such as

and the like, and (b) arylalkylene groups wherein only the alkyl portionforms the linkage between the

moiety and the-Gmoiety and the alkyl portion has aryl portions pending therefrom, suchas

and the like, or (iv) an alkylarylene group (including unsubstituted andsubstituted alkylarylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the aryl and the alkylportions of the alkylarylene group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms, inyet another embodiment with no more than about 12 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, such astolyl, phenylethyl, or the like, including (a) alkylarylene groupswherein both the aryl and the alkyl portions form the linkage betweenthe

moiety and the-Gmoiety, such as

and the like, and (b) alkylarylene groups wherein only the aryl portionforms the linkage between the

moiety and the-Gmoiety and the aryl portion has alkyl portions pending therefrom, suchas

and the like, with specific examples of R₆₆ including (but not beinglimited to) —CH₂—, —CH₂CH₂—, and the like, G is (1) a hydroxy group, (2)a carboxylic acid group, (3) an alkyl group (including linear, branched,saturated, unsaturated, cyclic, substituted, and unsubstituted alkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkyl group), in one embodiment with at least about 8 carbon atoms,in another embodiment with at least about 9 carbon atoms, in yet anotherembodiment with at least about 10 carbon atoms, in still anotherembodiment with at least about 11 carbon atoms, in another embodimentwith at least about 12 carbon atoms, in yet another embodiment with atleast about 13 carbon atoms, in still another embodiment with at leastabout 14 carbon atoms, in another embodiment with at least about 15carbon atoms, in yet another embodiment with at least about 16 carbonatoms, in still another embodiment with at least about 17 carbon atoms,in another embodiment with at least about 18 carbon atoms, in yetanother embodiment with at least about 19 carbon atoms, and in stillanother embodiment with at least about 20 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (4) an aryl group(including substituted and unsubstituted aryl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the aryl group), in oneembodiment with at least about 5 carbon atoms, in another embodimentwith at least about 6 carbon atoms, in yet another embodiment with atleast about 7 carbon atoms, in still another embodiment with at leastabout 8 carbon atoms, in another embodiment with at least about 9 carbonatoms, in yet another embodiment with at least about 10 carbon atoms, instill another embodiment with at least about 11 carbon atoms, in anotherembodiment with at least about 12 carbon atoms, in yet anotherembodiment with at least about 13 carbon atoms, in still anotherembodiment with at least about 14 carbon atoms, in another embodimentwith at least about 15 carbon atoms, in yet another embodiment with atleast about 16 carbon atoms, in still another embodiment with at leastabout 17 carbon atoms, in another embodiment with at least about 18carbon atoms, in yet another embodiment with at least about 19 carbonatoms, and in still another embodiment with at least about 20 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 18 carbon atoms, and in yetanother embodiment with no more than about 12 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (5) an arylalkylgroup (including substituted and unsubstituted arylalkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either thearyl or the alkyl portion of the arylalkyl group), in one embodimentwith at least about 14 carbon atoms, in another embodiment with at leastabout 15 carbon atoms, in yet another embodiment with at least about 16carbon atoms, in still another embodiment with at least about 17 carbonatoms, in another embodiment with at least about 18 carbon atoms, in yetanother embodiment with at least about 19 carbon atoms, in still anotherembodiment with at least about 20 carbon atoms, in another embodimentwith at least about 21 carbon atoms, in yet another embodiment with atleast about 22 carbon atoms, in still another embodiment with at leastabout 23 carbon atoms, in another embodiment with at least about 24carbon atoms, in yet another embodiment with at least about 25 carbonatoms, and in still another embodiment with at least about 26 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,although the number of carbon atoms can be outside of these ranges, (6)an alkylaryl group (including substituted and unsubstituted alkylarylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither the alkyl or the aryl portion of the alkylaryl group), in oneembodiment with at least about 14 carbon atoms, in another embodimentwith at least about 15 carbon atoms, in yet another embodiment with atleast about 16 carbon atoms, in still another embodiment with at leastabout 17 carbon atoms, in another embodiment with at least about 18carbon atoms, in yet another embodiment with at least about 19 carbonatoms, in still another embodiment with at least about 20 carbon atoms,in another embodiment with at least about 21 carbon atoms, in yetanother embodiment with at least about 22 carbon atoms, in still anotherembodiment with at least about 23 carbon atoms, in another embodimentwith at least about 24 carbon atoms, in yet another embodiment with atleast about 25 carbon atoms, and in still another embodiment with atleast about 26 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (7) a group of the formula

(8) a group of the formula

(9) a group of the formula

or (10) a group of the formula

R₇ is (i) an alkyl group (including linear, branched, saturated,unsaturated, cyclic, substituted, and unsubstituted alkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the alkylgroup), in one embodiment with at least about 1 carbon atom, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (ii) an aryl group(including substituted and unsubstituted aryl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the aryl group), in oneembodiment with at least about 5 carbon atoms, and in another embodimentwith at least about 6 carbon atoms, and in one embodiment with no morethan about 50 carbon atoms, in another embodiment with no more thanabout 18 carbon atoms, and in yet another embodiment with no more thanabout 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (iii) an arylalkyl group (including substitutedand unsubstituted arylalkyl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either the aryl or the alkyl portion of thearylalkyl group), in one embodiment with at least about 6 carbon atoms,and in another embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as benzyl or thelike, or (iv) an alkylaryl group (including substituted andunsubstituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either the alkyl or the aryl portion of thealkylaryl group), in one embodiment with at least about 6 carbon atoms,and in another embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as tolyl or thelike, R₈ is (i) a hydrogen atom, (ii) an alkyl group (including linear,branched, saturated, unsaturated, cyclic, substituted, and unsubstitutedalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in the alkyl group), in one embodiment with at least about 1carbon atom, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms,and in yet another embodiment with no more than about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges,(iii) an aryl group (including substituted and unsubstituted arylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least about 5 carbon atoms,and in another embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (iv) an arylalkyl group(including substituted and unsubstituted arylalkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either the aryl or thealkyl portion of the arylalkyl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms,and in yet another embodiment with no more than about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, or (v) an alkylaryl group (including substitutedand unsubstituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either the alkyl or the aryl portion of thealkylaryl group), in one embodiment with at least about 6 carbon atoms,and in another embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as tolyl or thelike, X is —O— or —NR₉—, and R₉ is (i) a hydrogen atom, (ii) an alkylgroup (including linear, branched, saturated, unsaturated, cyclic,substituted, and unsubstituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the alkyl group), in one embodimentwith at least about 1 carbon atom, and in one embodiment with no morethan about 50 carbon atoms, in another embodiment with no more thanabout 18 carbon atoms, and in yet another embodiment with no more thanabout 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (iii) an aryl group (including substituted andunsubstituted aryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the aryl group), in one embodiment with at least about5 carbon atoms, and in another embodiment with at least about 6 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 18 carbon atoms, and in yetanother embodiment with no more than about 12 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (iv) an arylalkylgroup (including substituted and unsubstituted arylalkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either thearyl or the alkyl portion of the arylalkyl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 18carbon atoms, and in yet another embodiment with no more than about 12carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as benzyl or the like, or (v) an alkylaryl group(including substituted and unsubstituted alkylaryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either the alkyl or thearyl portion of the alkylaryl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms,and in yet another embodiment with no more than about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas tolyl or the like, and wherein the substituents on the substitutedalkyl, alkylene, aryl, arylene, arylalkyl, arylalkylene, alkylaryl, andalkylarylene groups can be (but are not limited to) hydroxy groups,halogen atoms, amine groups, imine groups, ammonium groups, cyanogroups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ketone groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acidgroups, sulfide groups, sulfoxide groups, phosphine groups, phosphoniumgroups, phosphate groups, nitrile groups, mercapto groups, nitro groups,nitroso groups, sulfone groups, acyl groups, acid anhydride groups,azide groups, azo groups, cyanato groups, isocyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring.

It should be noted that since hetero atoms can be present in the alkyl,alkylene, aryl, arylene, arylalkyl, arylalkylene, alkylaryl, andalkylarylene groups, these groups also include alkoxy, alkyleneoxy,aryloxy, aryleneoxy, arylalkyloxy, arylalkyleneoxy, alkylaryloxy,alkylaryleneoxy, and the like, including those wherein an oxygen atomthereof is the point of attachment of the R group, and including (butnot limited to) those of the formulae—(C_(a)H_(2a)O)bR₁₀and—(OC_(a)H_(2a))bOR₁₀wherein a is an integer representing the number of carbon atoms in thealkyleneoxy, aryleneoxy, arylalkyleneoxy, or alkylaryleneoxy group,being in various embodiments 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32,33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or50, although the value of a can be outside of these ranges, b is aninteger representing the number of repeat alkyleneoxy, aryleneoxy,arylalkyleneoxy, or alkylaryleneoxy units, being in one embodiment atleast 1, in another embodiment at least about 2, in yet anotherembodiment at least about 5, and in still another embodiment at leastabout 10, and being in one embodiment no more than about 200, in anotherembodiment no more than about 150, in yet another embodiment no morethan about 100, and in still another embodiment no more than about 50,although the value of b can be outside of these ranges, and R₁₀ is (i) ahydrogen atom, (ii) an alkyl group (including linear, branched,saturated, unsaturated, cyclic, unsubstituted, and substituted alkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkyl group), in one embodiment with at least about 1 carbon atom,in another embodiment with at least about 2 carbon atoms, in anotherembodiment with at least about 4 carbon atoms, in yet another embodimentwith at least about 6 carbon atoms, in still another embodiment with atleast about 8 carbon atoms, in another embodiment with at least about 10carbon atoms, in yet another embodiment with at least about 12 carbonatoms, in still another embodiment with at least about 14 carbon atoms,in another embodiment with at least about 16 carbon atoms, in yetanother embodiment with at least about 18 carbon atoms, in still anotherembodiment with at least about 20 carbon atoms, in another embodimentwith at least about 22 carbon atoms, in yet another embodiment with atleast about 24 carbon atoms, in still another embodiment with at leastabout 26 carbon atoms, in another embodiment with at least about 28carbon atoms, in yet another embodiment with at least about 30 carbonatoms, in still another embodiment with at least about 32 carbon atoms,in another embodiment with at least about 34 carbon atoms, in yetanother embodiment with at least about 36 carbon atoms, in still anotherembodiment with at least about 38 carbon atoms, in another embodimentwith at least about 40 carbon atoms, in yet another embodiment with atleast about 42 carbon atoms, in still another embodiment with at leastabout 44 carbon atoms, in another embodiment with at least about 46carbon atoms, in yet another embodiment with at least about 48 carbonatoms, and in still another embodiment with at least about 50 carbonatoms, and in one embodiment with no more than about 100 carbon atoms,in another embodiment with no more than about 70 carbon atoms, in yetanother embodiment with no more than about 60 carbon atoms, and in stillanother embodiment with no more than about 50 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (iii) an arylgroup (including unsubstituted and substituted aryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the aryl group), in oneembodiment with at least about 6 carbon atoms, in another embodimentwith at least about 10 carbon atoms, in yet another embodiment with atleast about 13 carbon atoms, in still another embodiment with at leastabout 14 carbon atoms, in another embodiment with at least about 16carbon atoms, in yet another embodiment with at least about 18 carbonatoms, in still another embodiment with at least about 20 carbon atoms,in another embodiment with at least about 22 carbon atoms, in yetanother embodiment with at least about 24 carbon atoms, in still anotherembodiment with at least about 26 carbon atoms, in another embodimentwith at least about 28 carbon atoms, in yet another embodiment with atleast about 30 carbon atoms, in still another embodiment with at leastabout 32 carbon atoms, in another embodiment with at least about 34carbon atoms, in yet another embodiment with at least about 36 carbonatoms, in still another embodiment with at least about 38 carbon atoms,in another embodiment with at least about 40 carbon atoms, in yetanother embodiment with at least about 42 carbon atoms, in still anotherembodiment with at least about 44 carbon atoms, in another embodimentwith at least about 46 carbon atoms, in yet another embodiment with atleast about 48 carbon atoms, and in still another embodiment with atleast about 50 carbon atoms, and in one embodiment with no more thanabout 100 carbon atoms, in another embodiment with no more than about 75carbon atoms, in yet another embodiment with no more than about 60carbon atoms, and in still another embodiment with no more than about 50carbon atoms, although the number of carbon atoms can be outside ofthese ranges, (iv) an arylalkyl group (including unsubstituted andsubstituted arylalkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the arylalkyl group), in one embodiment with at least about 6carbon atoms, in another embodiment with at least about 7 carbon atoms,in yet another embodiment with at least about 8 carbon atoms, in anotherembodiment with at least about 10 carbon atoms, in yet anotherembodiment with at least about 12 carbon atoms, in still anotherembodiment with at least about 14 carbon atoms, in another embodimentwith at least about 16 carbon atoms, in yet another embodiment with atleast about 18 carbon atoms, in still another embodiment with at leastabout 20 carbon atoms, in another embodiment with at least about 22carbon atoms, in yet another embodiment with at least about 24 carbonatoms, in still another embodiment with at least about 26 carbon atoms,in another embodiment with at least about 28 carbon atoms, in yetanother embodiment with at least about 30 carbon atoms, in still anotherembodiment with at least about 32 carbon atoms, in another embodimentwith at least about 34 carbon atoms, in yet another embodiment with atleast about 36 carbon atoms, in another embodiment with at least about38 carbon atoms, in yet another embodiment with at least about 40 carbonatoms, in still another embodiment with at least about 42 carbon atoms,in another embodiment with at least about 44 carbon atoms, in yetanother embodiment with at least about 46 carbon atoms, in still anotherembodiment with at least about 48 carbon atoms, and in anotherembodiment with at least about 50 carbon atoms, and in one embodimentwith no more than about 200 carbon atoms, in another embodiment with nomore than about 100 carbon atoms, in yet another embodiment with no morethan about 60 carbon atoms, and in still another embodiment with no morethan about 50 carbon atoms, although the number of carbon atoms can beoutside of these ranges, or (v) an alkylaryl group (includingunsubstituted and substituted alkylaryl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either or both of the alkylportion and the aryl portion of the alkylaryl group), in one embodimentwith at least about 6 carbon atoms, in another embodiment with at leastabout 7 carbon atoms, in yet another embodiment with at least about 8carbon atoms, in another embodiment with at least about 10 carbon atoms,in yet another embodiment with at least about 12 carbon atoms, in stillanother embodiment with at least about 14 carbon atoms, in anotherembodiment with at least about 16 carbon atoms, in yet anotherembodiment with at least about 18 carbon atoms, in still anotherembodiment with at least about 20 carbon atoms, in another embodimentwith at least about 22 carbon atoms, in yet another embodiment with atleast about 24 carbon atoms, in still another embodiment with at leastabout 26 carbon atoms, in another embodiment with at least about 28carbon atoms, in yet another embodiment with at least about 30 carbonatoms, in still another embodiment with at least about 32 carbon atoms,in another embodiment with at least about 34 carbon atoms, in yetanother embodiment with at least about 36 carbon atoms, in anotherembodiment with at least about 38 carbon atoms, in yet anotherembodiment with at least about 40 carbon atoms, in still anotherembodiment with at least about 42 carbon atoms, in another embodimentwith at least about 44 carbon atoms, in yet another embodiment with atleast about 46 carbon atoms, in still another embodiment with at leastabout 48 carbon atoms, and in another embodiment with at least about 50carbon atoms, and in one embodiment with no more than about 200 carbonatoms, in another embodiment with no more than about 100 carbon atoms,in yet another embodiment with no more than about 60 carbon atoms, andin still another embodiment with no more than about 50 carbon atoms,although the number of carbon atoms can be outside of these ranges.

Further, since hetero atoms can be present in these groups, these groupsalso include heterocyclic groups.

In one specific embodiment, the total number of carbon atoms inR₁+R₂+R₃+R₄+R₅+(R₆ or R₆₆)+R₇+R₈+R₉ is no more than about 200, inanother embodiment no more than about 100, and in yet another embodimentno more than about 70, although the total number of carbon atoms can beoutside of these ranges.

In one specific embodiment, the total number of carbon atoms inR₁+R₂+R₃+R₄+R₅+(R₆ or R₆₆)+R₇+R₈+R₉ is at least about 12, in anotherembodiment at least about 13, in yet another embodiment at least about14, in still another embodiment at least about 15, in another embodimentat least about 16, in yet another embodiment at least about 17, in stillanother embodiment at least about 18, in another embodiment at leastabout 19, in yet another embodiment at least about 20, in yet anotherembodiment at least about 21, in another embodiment at least about 22,in yet another embodiment at least about 23, in yet another embodimentat least about 24, in another embodiment at least about 25, in yetanother embodiment at least about 26, in yet another embodiment at leastabout 27, in another embodiment at least about 28, in yet anotherembodiment at least about 29, in yet another embodiment at least about30, in another embodiment at least about 31, in yet another embodimentat least about 32, in yet another embodiment at least about 33, inanother embodiment at least about 34, in yet another embodiment at leastabout 35, in yet another embodiment at least about 36, in anotherembodiment at least about 37, in yet another embodiment at least about38, in yet another embodiment at least about 39, in another embodimentat least about 40, in yet another embodiment at least about 41, in yetanother embodiment at least about 42, in another embodiment at leastabout 43, in yet another embodiment at least about 44, in yet anotherembodiment at least about 45, in another embodiment at least about 46,in yet another embodiment at least about 47, and in yet anotherembodiment at least about 48, although the total number of carbon atomscan be outside of these ranges.

In one specific embodiment, G is (I) an alkyl group having in oneembodiment at least about 8 carbon atoms, in another embodiment at leastabout 9 carbon atoms, in yet another embodiment at least about 10 carbonatoms, in still another embodiment at least about 11 carbon atoms, inanother embodiment at least about 12 carbon atoms, in yet anotherembodiment at least about 13 carbon atoms, in still another embodimentat least about 14 carbon atoms, in another embodiment at least about 15carbon atoms, in yet another embodiment at least about 16 carbon atoms,in still another embodiment at least about 17 carbon atoms, in anotherembodiment at least about 18 carbon atoms, in yet another embodiment atleast about 19 carbon atoms, in still another embodiment at least about20 carbon atoms, in another embodiment at least about 21 carbon atoms,in yet another embodiment at least about 22 carbon atoms, in stillanother embodiment at least about 23 carbon atoms, in another embodimentat least about 24 carbon atoms, in yet another embodiment at least about25 carbon atoms, in still another embodiment at least about 26 carbonatoms, in another embodiment at least about 27 carbon atoms, in yetanother embodiment at least about 28 carbon atoms, in still anotherembodiment at least about 29 carbon atoms, in another embodiment atleast about 30 carbon atoms, in yet another embodiment at least about 31carbon atoms, and in still another embodiment at least about 32 carbonatoms, (II) an arylalkyl group having at least about 14 carbon atoms,wherein the alkyl portion thereof has in one embodiment at least about 8carbon atoms, in another embodiment at least about 9 carbon atoms, inyet another embodiment at least about 10 carbon atoms, in still anotherembodiment at least about 11 carbon atoms, in another embodiment atleast about 12 carbon atoms, in yet another embodiment at least about 13carbon atoms, in still another embodiment at least about 14 carbonatoms, in another embodiment at least about 15 carbon atoms, in yetanother embodiment at least about 16 carbon atoms, in still anotherembodiment at least about 17 carbon atoms, in another embodiment atleast about 18 carbon atoms, in yet another embodiment at least about 19carbon atoms, in still another embodiment at least about 20 carbonatoms, in another embodiment at least about 21 carbon atoms, in yetanother embodiment at least about 22 carbon atoms, in still anotherembodiment at least about 23 carbon atoms, in another embodiment atleast about 24 carbon atoms, in yet another embodiment at least about 25carbon atoms, in still another embodiment at least about 26 carbonatoms, in another embodiment at least about 27 carbon atoms, in yetanother embodiment at least about 28 carbon atoms, in still anotherembodiment at least about 29 carbon atoms, in another embodiment atleast about 30 carbon atoms, in yet another embodiment at least about 31carbon atoms, and in still another embodiment at least about 32 carbonatoms, (III) an alkylaryl group having at least about 14 carbon atoms,wherein the alkyl portion thereof has in one embodiment at least about 8carbon atoms, in another embodiment at least about 9 carbon atoms, inyet another embodiment at least about 10 carbon atoms, in still anotherembodiment at least about 11 carbon atoms, in another embodiment atleast about 12 carbon atoms, in yet another embodiment at least about 13carbon atoms, in still another embodiment at least about 14 carbonatoms, in another embodiment at least about 15 carbon atoms, in yetanother embodiment at least about 16 carbon atoms, in still anotherembodiment at least about 17 carbon atoms, in another embodiment atleast about 18 carbon atoms, in yet another embodiment at least about 19carbon atoms, in still another embodiment at least about 20 carbonatoms, in another embodiment at least about 21 carbon atoms, in yetanother embodiment at least about 22 carbon atoms, in still anotherembodiment at least about 23 carbon atoms, in another embodiment atleast about 24 carbon atoms, in yet another embodiment at least about 25carbon atoms, in still another embodiment at least about 26 carbonatoms, in another embodiment at least about 27 carbon atoms, in yetanother embodiment at least about 28 carbon atoms, in still anotherembodiment at least about 29 carbon atoms, in another embodiment atleast about 30 carbon atoms, in yet another embodiment at least about 31carbon atoms, and in still another embodiment at least about 32 carbonatoms, or (IV) a group of one of the formulae

wherein R₇ is (i) an alkyl group having in one embodiment at least about8 carbon atoms, in another embodiment at least about 9 carbon atoms, inyet another embodiment at least about 10 carbon atoms, in still anotherembodiment at least about 11 carbon atoms, in another embodiment atleast about 12 carbon atoms, in yet another embodiment at least about 13carbon atoms, in still another embodiment at least about 14 carbonatoms, in another embodiment at least about 15 carbon atoms, in yetanother embodiment at least about 16 carbon atoms, in still anotherembodiment at least about 17 carbon atoms, in another embodiment atleast about 18 carbon atoms, in yet another embodiment at least about 19carbon atoms, in still another embodiment at least about 20 carbonatoms, in another embodiment at least about 21 carbon atoms, in yetanother embodiment at least about 22 carbon atoms, in still anotherembodiment at least about 23 carbon atoms, in another embodiment atleast about 24 carbon atoms, in yet another embodiment at least about 25carbon atoms, in still another embodiment at least about 26 carbonatoms, in another embodiment at least about 27 carbon atoms, in yetanother embodiment at least about 28 carbon atoms, in still anotherembodiment at least about 29 carbon atoms, in another embodiment atleast about 30 carbon atoms, in yet another embodiment at least about 31carbon atoms, and in still another embodiment at least about 32 carbonatoms, (ii) an arylalkyl group having at least about 14 carbon atoms,wherein the alkyl portion thereof has in one embodiment at least about 8carbon atoms, in another embodiment at least about 9 carbon atoms, inyet another embodiment at least about 10 carbon atoms, in still anotherembodiment at least about 11 carbon atoms, in another embodiment atleast about 12 carbon atoms, in yet another embodiment at least about 13carbon atoms, in still another embodiment at least about 14 carbonatoms, in another embodiment at least about 15 carbon atoms, in yetanother embodiment at least about 16 carbon atoms, in still anotherembodiment at least about 17 carbon atoms, in another embodiment atleast about 18 carbon atoms, in yet another embodiment at least about 19carbon atoms, in still another embodiment at least about 20 carbonatoms, in another embodiment at least about 21 carbon atoms, in yetanother embodiment at least about 22 carbon atoms, in still anotherembodiment at least about 23 carbon atoms, in another embodiment atleast about 24 carbon atoms, in yet another embodiment at least about 25carbon atoms, in still another embodiment at least about 26 carbonatoms, in another embodiment at least about 27 carbon atoms, in yetanother embodiment at least about 28 carbon atoms, in still anotherembodiment at least about 29 carbon atoms, in another embodiment atleast about 30 carbon atoms, in yet another embodiment at least about 31carbon atoms, and in still another embodiment at least about 32 carbonatoms, or (iii) an alkylaryl group having at least about 14 carbonatoms, wherein the alkyl portion thereof has in one embodiment at leastabout 8 carbon atoms, in another embodiment at least about 9 carbonatoms, in yet another embodiment at least about 10 carbon atoms, instill another embodiment at least about 11 carbon atoms, in anotherembodiment at least about 12 carbon atoms, in yet another embodiment atleast about 13 carbon atoms, in still another embodiment at least about14 carbon atoms, in another embodiment at least about 15 carbon atoms,in yet another embodiment at least about 16 carbon atoms, in stillanother embodiment at least about 17 carbon atoms, in another embodimentat least about 18 carbon atoms, in yet another embodiment at least about19 carbon atoms, in still another embodiment at least about 20 carbonatoms, in another embodiment at least about 21 carbon atoms, in yetanother embodiment at least about 22 carbon atoms, in still anotherembodiment at least about 23 carbon atoms, in another embodiment atleast about 24 carbon atoms, in yet another embodiment at least about 25carbon atoms, in still another embodiment at least about 26 carbonatoms, in another embodiment at least about 27 carbon atoms, in yetanother embodiment at least about 28 carbon atoms, in still anotherembodiment at least about 29 carbon atoms, in another embodiment atleast about 30 carbon atoms, in yet another embodiment at least about 31carbon atoms, and in still another embodiment at least about 32 carbonatoms.

The above formula encompasses monomeric materials. In addition, theabove formula encompasses dimeric materials containing two moieties ofthe formula

wherein each G, independently of the other, is (1) an alkylene group(including linear, branched, saturated, unsaturated, cyclic,substituted, and unsubstituted alkylene groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the alkylene group), in oneembodiment with at least about 1 carbon atom, and in one embodiment withno more than about 50 carbon atoms, in another embodiment with no morethan about 18 carbon atoms, and in yet another embodiment with no morethan about 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (2) an arylene group (including unsubstitutedand substituted arylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in the arylene group), in one embodiment with atleast about 5 carbon atoms, and in another embodiment with at leastabout 6 carbon atoms, and in one embodiment with no more than about 50carbon atoms, in another embodiment with no more than about 18 carbonatoms, in yet another embodiment with no more than about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges, (3) an arylalkylene group (including unsubstituted andsubstituted arylalkylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the aryl and the alkylportions of the arylalkylene group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms, inyet another embodiment with no more than about 12 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, such asbenzylene or the like, including (a) arylalkylene groups wherein boththe aryl and the alkyl portions form the linkage between the two

moieties, such as

the like, and (b) arylalkylene groups wherein only the alkyl portionforms the linkage between the two

moieties, such as

and the like, (4) an alkylarylene group (including unsubstituted andsubstituted alkylarylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the aryl and the alkylportions of the alkylarylene group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms, inyet another embodiment with no more than about 12 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, such astolylene, phenylethylene, or the like, including (a) alkylarylene groupswherein both the aryl and the alkyl portions form the linkage betweenthe two

moieties, such as

and the like, and (b) alkylarylene groups wherein only the aryl portionforms the linkage between the two

moieties, such as

and the like, (5) a group of the formula

(6) a group of the formula

(7) a group of the formula

or (8) a group of the formula

wherein each R₇, independently of the other, is (i) an alkylene group(including linear, branched, saturated, unsaturated, cyclic,substituted, and unsubstituted alkylene groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the alkylene group), in oneembodiment with at least about 1 carbon atom, and in one embodiment withno more than about 50 carbon atoms, in another embodiment with no morethan about 18 carbon atoms, and in yet another embodiment with no morethan about 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (ii) an arylene group (including substitutedand unsubstituted arylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in the arylene group), in one embodiment with atleast about 5 carbon atoms, and in another embodiment with at leastabout 6 carbon atoms, and in one embodiment with no more than about 50carbon atoms, in another embodiment with no more than about 18 carbonatoms, and in yet another embodiment with no more than about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges, (iii) an arylalkylene group (including substituted andunsubstituted arylalkylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either the aryl or the alkyl portion of thearylalkylene group), in one embodiment with at least about 6 carbonatoms, and in another embodiment with at least about 7 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as benzylene or thelike, or (iv) an alkylarylene group (including substituted andunsubstituted alkylarylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either the alkyl or the aryl portion of thealkylarylene group), in one embodiment with at least about 6 carbonatoms, and in another embodiment with at least about 7 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 18 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as tolylene or thelike, each R₈, independently of the other, is (i) a hydrogen atom, (ii)an alkyl group (including linear, branched, saturated, unsaturated,cyclic, substituted, and unsubstituted alkyl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the alkyl group), in oneembodiment with at least about 1 carbon atom, and in one embodiment withno more than about 50 carbon atoms, in another embodiment with no morethan about 18 carbon atoms, and in yet another embodiment with no morethan about 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (iii) an aryl group (including substituted andunsubstituted aryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the aryl group), in one embodiment with at least about5 carbon atoms, and in another embodiment with at least about 6 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 18 carbon atoms, and in yetanother embodiment with no more than about 12 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (iv) an arylalkylgroup (including substituted and unsubstituted arylalkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either thearyl or the alkyl portion of the arylalkyl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 18carbon atoms, and in yet another embodiment with no more than about 12carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as benzyl or the like, or (v) an alkylaryl group(including substituted and unsubstituted alkylaryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either the alkyl or thearyl portion of the alkylaryl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms,and in yet another embodiment with no more than about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas tolyl or the like, each X, independently of the other, is —O— or—NR₉—, and each R₉, independently of the other, is (i) a hydrogen atom,(ii) an alkyl group (including linear, branched, saturated, unsaturated,cyclic, substituted, and unsubstituted alkyl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the alkyl group), in oneembodiment with at least about 1 carbon atom, and in one embodiment withno more than about 50 carbon atoms, in another embodiment with no morethan about 18 carbon atoms, and in yet another embodiment with no morethan about 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (iii) an aryl group (including substituted andunsubstituted aryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the aryl group), in one embodiment with at least about5 carbon atoms, and in another embodiment with at least about 6 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 18 carbon atoms, and in yetanother embodiment with no more than about 12 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (iv) an arylalkylgroup (including substituted and unsubstituted arylalkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either thearyl or the alkyl portion of the arylalkyl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 18carbon atoms, and in yet another embodiment with no more than about 12carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as benzyl or the like, or (v) an alkylaryl group(including substituted and unsubstituted alkylaryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either the alkyl or thearyl portion of the alkylaryl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 18 carbon atoms,and in yet another embodiment with no more than about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas tolyl or the like, and wherein the substituents on the substitutedalkyl, alkylene, aryl, arylene, arylalkyl, arylalkylene, alkylaryl, andalkylarylene groups can be (but are not limited to) hydroxy groups,halogen atoms, amine groups, imine groups, ammonium groups, cyanogroups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ketone groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acidgroups, sulfide groups, sulfoxide groups, phosphine groups, phosphoniumgroups, phosphate groups, nitrile groups, mercapto groups, nitro groups,nitroso groups, sulfone groups, acyl groups, acid anhydride groups,azide groups, azo groups, cyanato groups, isocyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring.

It should be noted that since hetero atoms can be present in the alkyl,alkylene, aryl, arylene, arylalkyl, arylalkylene, alkylaryl, andalkylarylene groups, these groups also include alkoxy, alkyleneoxy,aryloxy, aryleneoxy, arylalkyloxy, arylalkyleneoxy, alkylaryloxy,alkylaryleneoxy, and the like, including those wherein an oxygen atomthereof is the point of attachment of the R group, and including (butnot limited to) those of the formulae—(C_(a)H_(2a)O)b-wherein a is an integer representing the number of carbon atoms in thealkyleneoxy, aryleneoxy, arylalkyleneoxy, or alkylaryleneoxy group,being in various embodiments 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32,33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or50, although the value of a can be outside of these ranges, b is aninteger representing the number of repeat alkyleneoxy, aryleneoxy,arylalkyleneoxy, or alkylaryleneoxy groups, being in one embodiment atleast 1, in another embodiment at least about 2, in yet anotherembodiment at least about 5, and in still another embodiment at leastabout 10, and being in one embodiment no more than about 200, in anotherembodiment no more than about 150, in yet another embodiment no morethan about 100, and in still another embodiment no more than about 50,although the value of b can be outside of these ranges.

Further, since hetero atoms can be present in these groups, these groupsalso include heterocyclic groups.

Examples of such dimeric materials include (but are not limited to)those of the formulae

wherein R represents an alkyl, aryl, arylalkyl, or alkylaryl group asdefined hereinabove having no substituents thereon and no hetero atomstherein,

wherein R represents an alkyl, aryl, arylalkyl, or alkylaryl group asdefined hereinabove having no substituents thereon and no hetero atomstherein, and the like.

Similarly, the above formula encompasses trimeric, tetrameric, andhigher moieties as well as oligomeric materials and polymeric materials,said materials containing three or more moieties of the formula

wherein each R₁, R₂, R₃, R₄, R₅, R₆, R₆₆, G, m, n, and p, independentlyof the others, has the definitions for R₁, R₂, R₃, R₄, R₅, R₆, R₆₆, G,m, n, and p set forth hereinabove and can be either the same as ordifferent from one another, said moieties being linked by a central atomor group of atoms or bonded to a polymeric chain. These materials can bemade by processes analogous to those illustrated herein for themonomeric and dimeric compounds.

The compounds disclosed herein can be any of a wide variety of colors.In one specific embodiment, the compound is of a red color. In anotherspecific embodiment, the compound is of a magenta color.

The colorant compounds disclosed herein can be prepared by any desiredor effective method. Starting materials such as4-bromo-1:9-N-methylanthrapyridone, can be prepared as disclosed in, forexample, “British Intelligence Objectives Subcommittee Report 1484”,Publication Board No. 86139, Library of Congress, Washington, D.C.,1947, p. 46-47, the disclosure of which is totally incorporated byreference. This material is also commercially available from, forexample, Hangsu Aolunda High Tech Industry Co. Ltd., Shanghai, China.Further background on syntheses of starting materials and relatedcompounds is disclosed in, for example, U.S. Pat. No. 6,152,969, U.S.Pat. No. 5,340,910, U.S. Pat. No. 4,386,206, U.S. Pat. No. 4,745,174,and U.S. Pat. No. 2,644,821, the disclosures of each of which aretotally incorporated herein by reference.

Compounds of the formula

and compounds of the formula

can be prepared by analogous processes. Hereinafter, exemplary syntheticmethods will be provided for compounds of the formula

it is to be understood that these methods can also be used to preparecompounds of the formula

by employing analogous starting materials.

Compounds of the formula

can be prepared from brominated compounds of the formula

by reacting the brominated starting material with the correspondingaminobenzene having the desired alcohol group of the formula —R₆OH inthe presence of a base and heating, as follows:

The brominated starting material and the aminobenzene are present in anydesired or effective relative amounts, in one embodiment at least about1 mole of aminobenzene per every one mole of brominated startingmaterial, in another embodiment at least about 5 moles of aminobenzeneper every one mole of brominated starting material, and in yet anotherembodiment at least about 12 moles of aminobenzene per every one mole ofbrominated starting material, and in one embodiment no more than about20 moles of aminobenzene per every one mole of brominated startingmaterial, in another embodiment no more than about 15 moles ofaminobenzene per every one mole of brominated starting material, and inyet another embodiment no more than about 13 moles of aminobenzene perevery one mole of brominated starting material, although the relativeamounts of aminobenzene and brominated starting material can be outsideof these ranges.

Any desired or effective base can be employed. Examples of suitablebases include (but are not limited to) sodium carbonate, potassiumcarbonate, calcium carbonate, calcium oxide, zinc oxide, and the like,as well as mixtures thereof. The base is present in any desired oreffective amount, in one embodiment at least about 0.5 mole of base perevery one mole of brominated starting material, in another embodiment atleast about 1 mole of base per every one mole of brominated startingmaterial, and in yet another embodiment at least about 2 moles of baseper every one mole of brominated starting material, and in oneembodiment no more than about 5 moles of base per every one mole ofbrominated starting material, in another embodiment no more than about 4moles of base per every one mole of brominated starting material, and inyet another embodiment no more than about 3 moles of base per every onemole of brominated starting material, although the relative amounts ofaniline and brominated starting material can be outside of these ranges.

Optionally, if desired, a catalyst for the reaction can be employed,such as a copper salt, including (but not limited to) cupric acetate,copper sulfate, copper II acetate monohydrate, copper powder, and thelike, in any desired or effective amount.

While not required, if desired, an optional solvent can be employed. Ifused, any desired or effective solvent can be used, including polaraprotic solvents such as N-methylpyrrolidinone, dimethyl formamide,dimethyl sulfoxide, sulfolane, or the like, as well as mixtures thereof,in any desired or effective amount, in one embodiment in a ratio byweight of at least about 1 part by weight brominated starting materialper every hundred parts by weight solvent, and in one embodiment in aratio by weight of no more than about 20 parts by weight brominatedstarting material per every hundred parts by weight solvent, althoughthe relative amounts of solvent and brominated starting material can beoutside of these ranges.

The reaction mixture containing the aminobenzene and the brominatedstarting material is heated to any desirable or effective temperature toeffect the reaction, in one embodiment at least about 100° C., inanother embodiment at least about 120° C., and in yet another embodimentat least about 180° C., and in one embodiment no more than about 250°C., in another embodiment no more than about 200° C., and in yet anotherembodiment no more than about 190° C., although the temperature can beoutside of these ranges.

The reaction between the aminobenzene and the brominated startingmaterial is allowed to proceed for any desired or effective period oftime, in one embodiment at least about 10 minutes, in another embodimentat least about 1 hour, and in yet another embodiment at least about 1.5hour, and in one embodiment no more than about 4 days, in anotherembodiment no more than about 1 day, and in yet another embodiment nomore than about 2 hours, although the reaction time can be outside ofthese ranges.

Upon completion of the reaction, the compound of the formula

can be recovered by quenching the reaction mixture with a mixture ofacid and water, followed by filtration, washing, and drying. Any desiredor effective acid can be employed, such as hydrochloric acid, sulfuricacid, phosphoric acid, or the like, as well as mixtures thereof, in anydesired or effective concentration, in one specific embodiment at leastabout 1 percent by weight acid in water, and in one specific embodimentno more than about 20 percent by weight acid in water, although theconcentration can be outside of these ranges.

The alcohol-substituted compound of the formula

can be converted to an ester-substituted compound of the formula

by preparing a reaction mixture by admixing (1) the alcohol-substitutedcompound, (2) a solvent, and (3) an esterification compound such as ananhydride of the formula

in which reaction mixture upon heating is formed an ester-substitutedcompound as follows

The alcohol-substituted compound and the anhydride are present in anydesired or effective relative amounts, in one embodiment at least about1 mole of anhydride per every one mole of alcohol-substituted compound,and in one embodiment no more than about 1.1 moles of anhydride perevery one mole of alcohol-substituted compound, although the amount ofanhydride can be outside of these ranges.

Examples of suitable solvents include acetic acid, propionic acid,formic acid, butyric acid, dimethyl formamide, dimethyl sulfoxide,hexamethyl phosphorus triamide (HMPA), tetrahydrofuran, or the like, aswell as mixtures thereof. The solvent is present in any desired oreffective amount, in one embodiment at least about 25 grams ofalcohol-substituted compound per every one liter of solvent, and inanother embodiment at least about 100 grams of alcohol-substitutedcompound per every one liter of solvent, and in one embodiment no morethan about 200 grams of alcohol-substituted compound per every one literof solvent, although the amount of solvent can be outside of theseranges.

The reaction mixture containing the alcohol-substituted compound, thesolvent, and the anhydride is heated to any desirable or effectivetemperature, in one embodiment at least about 25° C., and in anotherembodiment at least about 40° C., and in one embodiment no more thanabout 100° C., and in another embodiment no more than about 60° C.,although the temperature can be outside of these ranges.

The reaction mixture containing the alcohol-substituted compound, thesolvent, and the anhydride is heated for any desirable or effectiveperiod of time, in one embodiment at least about 2.5 hours, and inanother embodiment at least about 3 hours, and in one embodiment no morethan about 5 hours, although the heating time can be outside of theseranges. Reaction completion can be determined by thin layerchromatography of the reaction mixture to detect the presence ofunreacted reactants.

The alcohol-substituted compound of the formula

can also be converted to an ester-substituted compound of the formula

by admixing (1) the alcohol-substituted compound, (2) an esterificationcompound such as a carboxylic acid of the formula R₇COOH, (3) a solvent,and (4) an optional esterification catalyst and heating the reactionmixture, as follows:

The alcohol-substituted compound and the carboxylic acid are present inany desired or effective relative amounts, in one embodiment at leastabout 0.9 mole of carboxylic acid per every one mole ofalcohol-substituted compound, in another embodiment at least about 0.95mole of carboxylic acid per mole of alcohol-substituted compound, and inyet another embodiment at least about 1 mole of carboxylic acid per moleof alcohol-substituted compound, and in one embodiment no more thanabout 2 moles of carboxylic acid per mole of alcohol-substitutedcompound, in another embodiment no more than about 1.05 moles ofcarboxylic acid per mole of alcohol-substituted compound, and in yetanother embodiment no more than about 1 mole of carboxylic acid per moleof alcohol-substituted compound, although the relative amounts ofcarboxylic acid and alcohol-substituted compound can be outside of theseranges.

When the optional esterification catalyst is present, any desired oreffective esterification catalyst can be used, such as para-toluenesulfonic acid, dibutyl tin dilaurate, or the like, as well as mixturesthereof. The esterification catalyst is present in any desired oreffective amount, in one embodiment at least about 0.05 mole ofesterification catalyst per every one mole of alcohol-substitutedcompound, and in one embodiment no more than about 0.5 mole ofesterification catalyst per mole of alcohol-substituted compound,although the amount of esterification catalyst can be outside of theseranges.

Any desired or effective solvent can be used. Examples of suitablesolvents include xylene, toluene, benzene, chlorobenzene, nitrobenzene,dichlorobenzene, and the like, as well as mixtures thereof. Thereactants are present in the solvent in any desired or effective amount,in one embodiment at least about 25 grams of alcohol-substitutedcompound per every one liter of solvent, in another embodiment at leastabout 50 grams of alcohol-substituted compound per every one liter ofsolvent, and in yet another embodiment at least about 100 grams ofalcohol-substituted compound per every one liter of solvent, and in oneembodiment no more than about 200 grams of alcohol-substituted compoundper every one liter of solvent, in another embodiment no more than about150 grams of alcohol-substituted compound per every one liter ofsolvent, and in yet another embodiment no more than about 100 grams ofalcohol-substituted compound per every one liter of solvent, althoughthe amount of solvent can be outside of these ranges.

The reaction mixture containing the alcohol-substituted compound, thecarboxylic acid, the solvent, and the optional esterification catalystis heated to any desirable or effective temperature, typically thereflux temperature of the selected solvent, in one embodiment at leastabout 100° C., and in one embodiment no more than about 130° C.,although the temperature can be outside of these ranges.

The reaction mixture containing the alcohol-substituted compound, thecarboxylic acid, the solvent, and the optional esterification catalystis heated for any desirable or effective period of time, in oneembodiment at least about 2 hours, in another embodiment at least about24 hours, and in one embodiment no more than about 72 hours, and inanother embodiment no more than about 48 hours, although the heatingtime can be outside of these ranges.

The compound of the formula

can be recovered from the reaction mixture as a solid by filtration,followed by washing and drying. If desired, purification can be carriedout by filtration, redissolution in the solvent, heating, cooling,precipitating the compound from the solution, filtering, washing thecompound with a solvent such as methanol, ethanol, or the like, andrepeating this cycle until thin layer chromatography of the collectedsolid indicates that there is no detectable unreacted reactant presentin the solid.

The alcohol-substituted compound of the formula

can be converted to a urethane-substituted compound of the formula

by reacting the alcohol-substituted compound with an isocyanate, asfollows:

Isocyanates react with alcohols to form urethanes. For example, amonoisocyanate reacts with an alcohol to form a urethane as follows:

wherein R_(a) and R_(b) each, independently of the other, is an alkylgroup (including linear, branched, saturated, unsaturated, cyclic,unsubstituted, and substituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the alkyl group), typically withfrom about 5 to about 100 carbon atoms, although the number of carbonatoms can be outside of this range, an aryl group (includingunsubstituted and substituted aryl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the aryl group), typically with fromabout 5 to about 20 carbon atoms, although the number of carbon atomscan be outside of this range, an arylalkyl group (includingunsubstituted and substituted arylalkyl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either or both of the alkylportion and the aryl portion of the arylalkyl group), typically withfrom about 6 to about 50 carbon atoms, although the number of carbonatoms can be outside of this range, or an alkylaryl group (includingunsubstituted and substituted alkylaryl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either or both of the alkylportion and the aryl portion of the alkylaryl group), typically withfrom about 6 to about 50 carbon atoms, although the number of carbonatoms can be outside of this range, and wherein the substituents on thesubstituted alkyl, alkylene, aryl, arylene, arylalkyl, arylalkylene,alkylaryl, and alkylarylene groups can be (but are not limited to)hydroxy groups, halogen atoms, amine groups, imine groups, ammoniumgroups, cyano groups, pyridine groups, pyridinium groups, ether groups,aldehyde groups, ketone groups, ester groups, amide groups, carbonylgroups, thiocarbonyl groups, sulfate groups, sulfonate groups, sulfidegroups, sulfoxide groups, phosphine groups, phosphonium groups,phosphate groups, nitrile groups, mercapto groups, nitro groups, nitrosogroups, sulfone groups, acyl groups, acid anhydride groups, azidegroups, azo groups, cyanato groups, isocyanato groups, thiocyanatogroups, isothiocyanato groups, mixtures thereof, and the like, whereintwo or more substituents can be joined together to form a ring.Diisocyanates react similarly; for example, isophorone diisocyanatereacts with two moles of alcohol to form a diurethane as follows:

Examples of suitable isocyanates include monoisocyanates, diisocyanates,triisocyanates, copolymers of a diisocyanate, copolymers of atriisocyanate, polyisocyanates (having more than three isocyanatefunctional groups), and the like, as well as mixtures thereof. Examplesof monoisocyanates include octadecylisocyanate; hexadecylisocyanate;octylisocyanate; butyl and t-butylisocyanate; cyclohexyl isocyanate;adamantyl isocyanate; ethylisocyanatoacetate; ethoxycarbonylisocyanate;phenylisocyanate; alphamethylbenzyl isocyanate; 2-phenylcyclopropylisocyanate; benzylisocyanate; 2-ethylphenylisocyanate;benzoylisocyanate; meta and para-tolylisocyanate; 2-, 3-, or4-nitrophenylisocyanates; 2-ethoxyphenyl isocyanate; 3-methoxyphenylisocyanate; 4-methoxyphenylisocyanate; ethyl 4-isocyanatobenzoate;2,6-dimethylphenylisocyante; 1-naphthylisocyanate;(naphthyl)ethylisocyantes; and the like, as well as mixtures thereof.Examples of diisocyanates include isophorone diisocyanate (IPDI);toluene diisocyanate (TDI); diphenylmethane-4,4′-diisocyanate (MDI);hydrogenated diphenylmethane-4,4′-diisocyanate (H12MDI); tetra-methylxylene diisocyanate (TMXDI); hexamethylene-1,6-diisocyanate (HDI);hexamethylene-1,6-diisocyanate; naphthalene-1,5-diisocyanate;3,3′-dimethoxy-4,4′-biphenyldiisocyanate;3,3′-dimethyl-4,4′-bimethyl-4,4′-biphenyldiisocyanate; phenylenediisocyanate; 4,4′-biphenyldiisocyanate; trimethylhexamethylenediisocyanate; tetramethylene xylene diisocyanate;4,4′-methylenebis(2,6-diethylphenyl isocyanate);1,12-diisocyanatododecane; 1,5-diisocyanato-2-methylpentane;1,4-diisocyanatobutane; dimer diisocyanate and cyclohexylenediisocyanate and its isomers; uretidione dimers of HDI; and the like, aswell as mixtures thereof. Examples of triisocyanates or theirequivalents include the trimethylolpropane trimer of TDI, and the like,isocyanurate trimers of TDI, HDI, IPDI, and the like, and biuret trimersof TDI, HDI, IPDI, and the like, as well as mixtures thereof. Examplesof higher isocyanate functionalities include copolymers of TDI/HDI, andthe like, and MDI oligomers, as well as mixtures thereof.

Any suitable reaction condition for making urethane compounds bycondensing alcohols with isocyanates can be used to prepare theurethane-substituted compounds. Typically (although not necessarily),the reaction is carried out at elevated temperatures (for example, fromabout 60 to about 160° C.) in the presence of an optional urethanereaction catalyst, such as dibutyl tin dilaurate, bismuthtris-neodecanoate, cobalt benzoate, lithium acetate, stannous octoate,triethylamine, or the like. In a specific embodiment, the reactionconditions are conducted in an inert atmosphere, such as argon ornitrogen gas or other suitable gases, to prevent oxidizing or yellowingof the reaction products and to prevent undesirable side reactions. Thereaction can employ an inert solvent, such as toluene or the like, orcan be performed neat (i.e., without a solvent). The mole ratio ofreactants is adjusted so that the isocyanate functionalities arecompletely consumed in the reaction with a slight molar excess ofalcohol-substituted colorant typically remaining. The reactants can beadded together in any order and/or added to the reaction as physicalmixtures. If desired, reaction conditions and the order of the additionof reactants can be controlled for several reasons, such as to provide acontrolled exothermic reaction, to tailor the distribution of moleculesin the antioxidant-containing material, or the like. When doing theseadjustments, the different reactivities to isocyanates of alcoholsversus amines can be employed, as well as the different reactivities ofthe two separate isocyanate groups on IPDI. See, for example, J. H.Saunders and K. C. Frisch's “Polyurethanes Part I, Chemistry” publishedby Interscience of New York, N.Y. in 1962 and Olin Chemicals' LUXATE® IMisophorone diisocyanate technical product information sheet, thedisclosures of each of which are totally incorporated herein byreference, which provide further explanation of this chemistry.

Compounds of the formula

can be prepared by first preparing a urea-substituted precursor from adiamino compound by reacting the diamino compound with an isocyanate,either neat or, optionally, in the presence of a solvent, as follows:

Thereafter, the resulting urea precursor can be reacted with abrominated compound of the formula

by reacting the brominated starting material with the urea precursor inthe presence of a base and an optional catalyst and heating, as follows:

The diamino compound and the isocyanate are present in any desired oreffective relative amounts, in one embodiment at least about 0.85 moleof isocyanate group per every one mole of diamino compound, in anotherembodiment at least about 0.95 mole of isocyanate group per every onemole of diamino compound, and in yet another embodiment at least about0.99 mole of isocyanate group per every one mole of diamino compound,and in one embodiment no more than about 1.02 moles of isocyanate groupper every one mole of diamino compound, in another embodiment no morethan about 1.01 moles of isocyanate group per every one mole of diaminocompound, and in yet another embodiment no more than about 1.005 molesof isocyanate group per every one mole of diamino compound, although therelative amounts of diamino compound and isocyanate group can be outsideof these ranges.

The brominated starting material and the urea precursor are present inany desired or effective relative amounts, in one embodiment at leastabout 1 mole of urea precursor per every one mole of brominated startingmaterial, in another embodiment at least about 5 moles of urea precursorper every one mole of brominated starting material, and in yet anotherembodiment at least about 12 moles of urea precursor per every one moleof brominated starting material, and in one embodiment no more thanabout 20 moles of urea precursor per every one mole of brominatedstarting material, in another embodiment no more than about 15 moles ofurea precursor per every one mole of brominated starting material, andin yet another embodiment no more than about 13 moles of urea precursorper every one mole of brominated starting material, although therelative amounts of urea precursor and brominated starting material canbe outside of these ranges.

Any desired or effective base can be employed. Examples of suitablebases include (but are not limited to) sodium carbonate, potassiumcarbonate, calcium carbonate, calcium oxide, zinc oxide, and the like,as well as mixtures thereof. The base is present in any desired oreffective amount, in one embodiment at least about 0.5 mole of base perevery one mole of brominated starting material, in another embodiment atleast about 1 mole of base per every one mole of brominated startingmaterial, and in yet another embodiment at least about 2 moles of baseper every one mole of brominated starting material, and in oneembodiment no more than about 5 moles of base per every one mole ofbrominated starting material, in another embodiment no more than about 4moles of base per every one mole of brominated starting material, and inyet another embodiment no more than about 3 moles of base per every onemole of brominated starting material, although the relative amounts ofbase and brominated starting material can be outside of these ranges.

When an optional solvent is employed for the reaction between thebrominated starting material and the urea precursor, any desired oreffective solvent can be employed, such as xylene, toluene, benzene,chlorobenzene, nitrobenzene, dichlorobenzene, N-methylpyrrolidinone,dimethyl formamide, dimethyl sulfoxide, sulfolane, hexanol, octanol, orthe like, as well as mixtures thereof.

When an optional catalyst is employed, any desired or effective catalystcan be employed, including copper salts, such as cupric acetate, coppersulfate, copper II acetate monohydrate, copper powder, and the like, aswell as mixtures thereof.

The reaction mixture containing the brominated starting material, theurea precursor, the optional solvent, the base, and the optionalcatalyst is heated to any desired or effective temperature, typicallythe reflux temperature of the selected solvent, in one embodiment atleast about 100° C., and in one embodiment no more than about 200° C.,although the temperature can be outside of these ranges.

The reaction mixture is heated for any desired or effective period oftime, in one embodiment at least about 2 hours, and in anotherembodiment at least about 24 hours, and in one embodiment no more thanabout 72 hours, and in another embodiment no more than about 48 hours,although the heating time can be outside of these ranges.

The urea-substituted colorant compound can be recovered from thereaction mixture as a solid by filtration, followed by washing anddrying. If desired, purification can be carried out by filtration,redissolution in the solvent, heating, cooling, precipitating thecolorant from the solution, filtering, washing the colorant with asolvent such as methanol, ethanol, or the like, and repeating this cycleuntil thin layer chromatography of the collected solid indicates thatthere is no detectable unreacted reactant present in the solid.

Compounds of the formula

can be prepared from brominated compounds of the formula

by reacting the brominated starting material with the correspondingaminobenzene having the desired acid group of the formula —R₆COOH,generally with an excess of the aminobenzene adduct, either neat or,optionally, in the presence of a solvent, at elevated temperatures.Workup usually entails quenching in water if run neat or in a watersoluble solvent, filtering, washing, and drying, or if run in a waterinsoluble solvent, cooling and allowing the product to precipitatefollowed by filtering, washing, and drying. The reaction proceeds asfollows:

The brominated starting material and the aminobenzene are present in anydesired or effective relative amounts, in one embodiment at least about1 mole of aminobenzene per every one mole of brominated startingmaterial, in another embodiment at least about 5 moles of aminobenzeneper every one mole of brominated starting material, and in yet anotherembodiment at least about 12 moles of aminobenzene per every one mole ofbrominated starting material, and in one embodiment no more than about20 moles of aminobenzene per every one mole of brominated startingmaterial, in another embodiment no more than about 15 moles ofaminobenzene per every one mole of brominated starting material, and inyet another embodiment no more than about 13 moles of aminobenzene perevery one mole of brominated starting material, although the relativeamounts of aminobenzene and brominated starting material can be outsideof these ranges.

Any desired or effective base can be employed. Examples of suitablebases include (but are not limited to) sodium carbonate, potassiumcarbonate, calcium carbonate, calcium oxide, zinc oxide, and the like,as well as mixtures thereof. The base is present in any desired oreffective amount, in one embodiment at least about 0.5 mole of base perevery one mole of brominated starting material, in another embodiment atleast about 1 mole of base per every one mole of brominated startingmaterial, and in yet another embodiment at least about 2 moles of baseper every one mole of brominated starting material, and in oneembodiment no more than about 5 moles of base per every one mole ofbrominated starting material, in another embodiment no more than about 4moles of base per every one mole of brominated starting material, and inyet another embodiment no more than about 3 moles of base per every onemole of brominated starting material, although the relative amounts ofaniline and brominated starting material can be outside of these ranges.

Optionally, if desired, a catalyst for the reaction can be employed,such as a copper salt, including (but not limited to) cupric acetate,copper sulfate, copper II acetate monohydrate, copper powder, and thelike, in any desired or effective amount.

While not required, if desired, an optional solvent can be employed. Ifused, any desired or effective solvent can be used, including polaraprotic solvents such as N-methylpyrrolidinone, dimethyl formamide,dimethyl sulfoxide, sulfolane, or the like, as well as mixtures thereof,in any desired or effective amount, in one embodiment in a ratio byweight of at least about 1 part by weight brominated starting materialper every hundred parts by weight solvent, and in one embodiment in aratio by weight of no more than about 20 parts by weight brominatedstarting material per every hundred parts by weight solvent, althoughthe relative amounts of solvent and brominated starting material can beoutside of these ranges.

The reaction mixture containing the aminobenzene and the brominatedstarting material is heated to any desirable or effective temperature toeffect the reaction, in one embodiment at least about 100° C., inanother embodiment at least about 120° C., and in yet another embodimentat least about 180° C., and in one embodiment no more than about 250°C., in another embodiment no more than about 200° C., and in yet anotherembodiment no more than about 190° C., although the temperature can beoutside of these ranges.

The reaction between the aminobenzene and the brominated startingmaterial is allowed to proceed for any desired or effective period oftime, in one embodiment at least about 10 minutes, in another embodimentat least about 1 hour, and in yet another embodiment at least about 1.5hour, and in one embodiment no more than about 4 days, in anotherembodiment no more than about 1 day, and in yet another embodiment nomore than about 2 hours, although the reaction time can be outside ofthese ranges.

Upon completion of the reaction, the compound of the formula

can be recovered by quenching the reaction mixture with a mixture ofacid and water, followed by filtration, washing, and drying. Any desiredor effective acid can be employed, such as hydrochloric acid, sulfuricacid, phosphoric acid, or the like, as well as mixtures thereof, in anydesired or effective concentration, in one specific embodiment at leastabout 1 percent by weight acid in water, and in one specific embodimentno more than about 20 percent by weight acid in water, although theconcentration can be outside of these ranges.

The acid-substituted compound of the formula

can be converted to an ester-substituted compound of the formula

by reacting the acid-substituted compound with an alcohol of the formulaR₇—OH, an optional solvent, and an optional esterification catalyst andheating, as follows:

The acid-substituted compound and the alcohol are present in any desiredor effective relative amounts, in one embodiment at least about 1 moleof alcohol per every one mole of acid-substituted compound, in anotherembodiment at least about 1.05 moles of alcohol per every one mole ofacid-substituted compound, and in yet another embodiment at least about1.1 moles of alcohol per every one mole of acid-substituted compound,and in one embodiment no more than about 2 moles of alcohol per everyone mole of acid-substituted compound, in another embodiment no morethan about 1.5 moles of alcohol per every one mole of acid-substitutedcompound, and in yet another embodiment no more than about 1.25 moles ofalcohol per every one mole of acid-substituted compound, although therelative amounts of acid-substituted compound and alcohol can be outsideof these ranges.

When the optional esterification catalyst is present, any desired oreffective esterification catalyst can be used, such as para-toluenesulfonic acid, dibutyl tin dilaurate, or the like, as well as mixturesthereof. The esterification catalyst is present in any desired oreffective amount, in one embodiment at least about 0.05 mole ofesterification catalyst per every one mole of alcohol, and in oneembodiment no more than about 0.5 mole of esterification catalyst permole of alcohol, although the amount of esterification catalyst can beoutside of these ranges.

When present, any desired or effective solvent can be used. Examples ofsuitable solvents include xylene, toluene, benzene, chlorobenzene,nitrobenzene, dichlorobenzene, and the like, as well as mixturesthereof. When the optional solvent is used, the reactants are present inthe solvent in any desired or effective amount, in one embodiment atleast about 25 grams of alcohol per every one liter of solvent, inanother embodiment at least about 50 grams of alcohol per every oneliter of solvent, and in yet another embodiment at least about 100 gramsof alcohol per every one liter of solvent, and in one embodiment no morethan about 200 grams of alcohol per every one liter of solvent, inanother embodiment no more than about 150 grams of alcohol per every oneliter of solvent, and in yet another embodiment no more than about 100grams of alcohol per every one liter of solvent, although the amount ofsolvent can be outside of these ranges.

The reaction mixture containing the alcohol, the acid-substitutedcompound, the optional solvent, and the optional esterification catalystis heated to any desirable or effective temperature, typically thereflux temperature of the selected solvent, in one embodiment at leastabout 100° C., and in one embodiment no more than about 130° C.,although the temperature can be outside of these ranges.

The reaction mixture containing the alcohol, the acid-substitutedcompound, the optional solvent, and the optional esterification catalystis heated for any desirable or effective period of time, in oneembodiment at least about 2 hours, in another embodiment at least about24 hours, and in one embodiment no more than about 72 hours, and inanother embodiment no more than about 48 hours, although the heatingtime can be outside of these ranges.

The esterified compound can be recovered from the reaction mixture as asolid by filtration, followed by washing and drying. If desired,purification can be carried out by filtration, redissolution in thesolvent, heating, cooling, precipitating the colorant from the solution,filtering, washing the compound with a solvent such as methanol,ethanol, or the like, and repeating this cycle until thin layerchromatography of the collected solid indicates that there is nodetectable unreacted reactant present in the solid.

The acid-substituted compound of the formula

can be converted to an amide-substituted compound of the formula

by reacting the acid-substituted compound with an amine of the formulaR₇—NH₂, an optional solvent, and an optional amidification catalyst andheating, as follows:

The acid-substituted compound and the amine are present in any desiredor effective relative amounts, in one embodiment at least about 1 moleof amine per every one mole of acid-substituted compound, in anotherembodiment at least about 1.05 moles of amine per every one mole ofacid-substituted compound, and in yet another embodiment at least about1.1 moles of amine per every one mole of acid-substituted compound, andin one embodiment no more than about 2 moles of amine per every one moleof acid-substituted compound, in another embodiment no more than about1.5 moles of amine per every one mole of acid-substituted compound, andin yet another embodiment no more than about 1.25 moles of amine perevery one mole of acid-substituted compound, although the relativeamounts of acid-substituted compound and amine can be outside of theseranges.

When the optional amidification catalyst is present, any desired oreffective amidification catalyst can be used, such as phosphoric acid orthe like. The amidification catalyst is present in any desired oreffective amount, in one embodiment at least about 0.05 mole ofamidification catalyst per every one mole of amine, and in oneembodiment no more than about 0.5 mole of amidification catalyst permole of amine, although the amount of amidification catalyst can beoutside of these ranges.

When present, any desired or effective solvent can be used. Examples ofsuitable solvents include xylene, toluene, benzene, chlorobenzene,nitrobenzene, dichlorobenzene, and the like, as well as mixturesthereof. When the optional solvent is used, the reactants are present inthe solvent in any desired or effective amount, in one embodiment atleast about 25 grams of amine per every one liter of solvent, in anotherembodiment at least about 50 grams of amine per every one liter ofsolvent, and in yet another embodiment at least about 100 grams of amineper every one liter of solvent, and in one embodiment no more than about200 grams of amine per every one liter of solvent, in another embodimentno more than about 150 grams of amine per every one liter of solvent,and in yet another embodiment no more than about 100 grams of amine perevery one liter of solvent, although the amount of solvent can beoutside of these ranges.

The reaction mixture containing the amine, the acid-substitutedcompound, the optional solvent, and the optional amidification catalystis heated to any desirable or effective temperature, typically thereflux temperature of the selected solvent, in one embodiment at leastabout 100° C., and in one embodiment no more than about 200° C.,although the temperature can be outside of these ranges.

The reaction mixture containing the amine, the acid-substitutedcompound, the optional solvent, and the optional amidification catalystis heated for any desirable or effective period of time, in oneembodiment at least about 2 hours, in another embodiment at least about24 hours, and in one embodiment no more than about 72 hours, and inanother embodiment no more than about 48 hours, although the heatingtime can be outside of these ranges.

The amidified compound can be recovered from the reaction mixture as asolid by filtration, followed by washing and drying. If desired,purification can be carried out by filtration, redissolution in thesolvent, heating, cooling, precipitating the colorant from the solution,filtering, washing the colorant with a solvent such as methanol,ethanol, or the like, and repeating this cycle until thin layerchromatography of the collected solid indicates that there is nodetectable unreacted reactant present in the solid.

The acid-substituted compound of the formula

can also be converted to an amide-substituted compound of the formula

by reacting the acid-substituted compound with an isocyanate of theformula R₇—NCO, optionally in the presence of a catalyst, either neator, optionally, in the presence of a solvent, at elevated temperaturesas follows:

The carboxylic acid-substituted compound and the isocyanate are presentin any desired or effective relative amounts, in one embodiment at leastabout 1 mole of isocyanate group per every one mole of carboxylicacid-substituted compound, in another embodiment at least about 1.05moles of isocyanate group per every one mole of carboxylicacid-substituted compound, and in yet another embodiment at least about1.1 moles of isocyanate group per every one mole of carboxylicacid-substituted compound, and in one embodiment no more than about 2moles of isocyanate group per every one mole of carboxylicacid-substituted compound, in another embodiment no more than about 1.5moles of isocyanate group per every one mole of carboxylicacid-substituted compound, and in yet another embodiment no more thanabout 1.25 moles of isocyanate group per every one mole of carboxylicacid-substituted compound, although the relative amounts of carboxylicacid-substituted compound and isocyanate group can be outside of theseranges.

When the optional catalyst is present, any desired or effective catalystcan be used, such as dibutyl tin dilaurate or the like. The catalyst ispresent in any desired or effective amount, in one embodiment at leastabout 0.05 mole of catalyst per every one mole of isocyanate, and in oneembodiment no more than about 0.5 mole of catalyst per mole ofisocyanate, although the amount of catalyst can be outside of theseranges.

When present, any desired or effective aprotic solvent can be used.Examples of suitable solvents include xylene, toluene, benzene,chlorobenzene, nitrobenzene, dichlorobenzene, and the like, as well asmixtures thereof. When the optional solvent is used, the reactants arepresent in the solvent in any desired or effective amount, in oneembodiment at least about 25 grams of isocyanate per every one liter ofsolvent, in another embodiment at least about 50 grams of isocyanate perevery one liter of solvent, and in yet another embodiment at least about100 grams of isocyanate per every one liter of solvent, and in oneembodiment no more than about 200 grams of isocyanate per every oneliter of solvent, in another embodiment no more than about 150 grams ofisocyanate per every one liter of solvent, and in yet another embodimentno more than about 100 grams of isocyanate per every one liter ofsolvent, although the amount of solvent can be outside of these ranges.

The reaction mixture containing the isocyanate, the carboxylicacid-substituted compound, the optional solvent, and the optionalcatalyst is heated to any desired or effective temperature, typicallythe reflux temperature of the selected solvent, in one embodiment atleast about 100° C., and in one embodiment no more than about 200° C.,although the temperature can be outside of these ranges.

The reaction mixture containing the isocyanate, the carboxylicacid-substituted compound, the optional solvent, and the optionalcatalyst is heated for any desired or effective period of time, in oneembodiment at least about 2 hours, and in another embodiment at leastabout 24 hours, and in one embodiment no more than about 72 hours, andin another embodiment no more than about 48 hours, although the heatingtime can be outside of these ranges.

The amide-substituted compound can be recovered from the reactionmixture as a solid by filtration, followed by washing and drying. Ifdesired, purification can be carried out by filtration, redissolution inthe solvent, heating, cooling, precipitating the colorant from thesolution, filtering, washing the colorant with a solvent such asmethanol, ethanol, or the like, and repeating this cycle until thinlayer chromatography of the collected solid indicates that there is nodetectable unreacted reactant present in the solid.

Phase change inks as disclosed herein contain a phase change carriersystem or composition. The phase change carrier composition is typicallydesigned for use in either a direct printing mode or an indirect oroffset printing transfer system.

In the direct printing mode, the phase change carrier composition in oneembodiment contains one or more materials that enable the phase changeink (1) to be applied in a thin film of uniform thickness on the finalrecording substrate (such as paper, transparency material, and the like)when cooled to ambient temperature after printing directly to therecording substrate, (2) to be ductile while retaining sufficientflexibility so that the applied image on the substrate will not fractureupon bending, and (3) to possess a high degree of lightness, chroma,transparency, and thermal stability.

In an offset printing transfer or indirect printing mode, the phasechange carrier composition in one embodiment exhibits not only thecharacteristics desirable for direct printing mode inks, but alsocertain fluidic and mechanical properties desirable for use in such asystem, as described in, for example, U.S. Pat. No. 5,389,958 thedisclosure of which is totally incorporated herein by reference.

Any desired or effective carrier composition can be used. Examples ofsuitable ink carrier materials include fatty amides, such as monoamides,tetra-amides, mixtures thereof, and the like. Specific examples ofsuitable fatty amide ink carrier materials include stearyl stearamide, adimer acid based tetra-amide that is the reaction product of dimer acid,ethylene diamine, and stearic acid, a dimer acid based tetra-amide thatis the reaction product of dimer acid, ethylene diamine, and acarboxylic acid having at least about 36 carbon atoms, and the like, aswell as mixtures thereof. When the fatty amide ink carrier is a dimeracid based tetra-amide that is the reaction product of dimer acid,ethylene diamine, and a carboxylic acid having at least about 36 carbonatoms, the carboxylic acid is of the general formula

wherein R is an alkyl group, including linear, branched, saturated,unsaturated, and cyclic alkyl groups, said alkyl group in one embodimenthaving at least about 36 carbon atoms, in another embodiment having atleast about 40 carbon atoms, said alkyl group in one embodiment havingno more than about 200 carbon atoms, in another embodiment having nomore than about 150 carbon atoms, and in yet another embodiment havingno more than about 100 carbon atoms, although the number of carbon atomscan be outside of these ranges. Carboxylic acids of this formula arecommercially available from, for example, Baker Petrolite, Tulsa, Okla.,and can also be prepared as described in Example 1 of U.S. Pat. No.6,174,937, the disclosure of which is totally incorporated herein byreference. Further information on fatty amide carrier materials isdisclosed in, for example, U.S. Pat. No. 4,889,560, U.S. Pat. No.4,889,761, U.S. Pat. No. 5,194,638, U.S. Pat. No. 4,830,671, U.S. Pat.No. 6,174,937, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,597,856, U.S.Pat. No. 6,174,937, and British Patent GB 2 238 792, the disclosures ofeach of which are totally incorporated herein by reference.

Also suitable as phase change ink carrier materials areisocyanate-derived resins and waxes, such as urethane isocyanate-derivedmaterials, urea isocyanate-derived materials, urethane/ureaisocyanate-derived materials, mixtures thereof, and the like. Furtherinformation on isocyanate-derived carrier materials is disclosed in, forexample, U.S. Pat. No. 5,750,604, U.S. Pat. No. 5,780,528, U.S. Pat. No.5,782,966, U.S. Pat. No. 5,783,658, U.S. Pat. No. 5,827,918, U.S. Pat.No. 5,830,942, U.S. Pat. No. 5,919,839, U.S. Pat. No. 6,255,432, U.S.Pat. No. 6,309,453, British Patent GB 2 294 939, British Patent GB 2 305928, British Patent GB 2 305 670, British Patent GB 2 290 793, PCTPublication WO 94/14902, PCT Publication WO 97/12003, PCT Publication WO97/13816, PCT Publication WO 96/14364, PCT Publication WO 97/33943, andPCT Publication WO 95/04760, the disclosures of each of which aretotally incorporated herein by reference.

Mixtures of fatty amide materials and isocyanate-derived materials canalso be employed as the ink carrier composition.

Additional suitable phase change ink carrier materials includeparaffins, microcrystalline waxes, polyethylene waxes, ester waxes,amide waxes, fatty acids, fatty alcohols, fatty amides and other waxymaterials, sulfonamide materials, resinous materials made from differentnatural sources (such as, for example, tall oil rosins and rosinesters), and many synthetic resins, oligomers, polymers and copolymers,such as ethylene/vinyl acetate copolymers, ethylene/acrylic acidcopolymers, ethylene/vinyl acetate/acrylic acid copolymers, copolymersof acrylic acid with polyamides, and the like, ionomers, and the like,as well as mixtures thereof. One or more of these materials can also beemployed in a mixture with a fatty amide material and/or anisocyanate-derived material.

In one specific embodiment, the phase change ink carrier comprises (a) apolyethylene wax, present in the ink in an amount in one embodiment ofat least about 25 percent by weight of the ink, in another embodiment ofat least about 30 percent by weight of the ink, and in yet anotherembodiment of at least about 37 percent by weight of the ink, and in oneembodiment of no more than about 60 percent by weight of the ink, inanother embodiment of no more than about 53 percent by weight of theink, and in yet another embodiment of no more than about 48 percent byweight of the ink, although the amount can be outside of these ranges;(b) a stearyl stearamide wax, present in the ink in an amount in oneembodiment of at least about 8 percent by weight of the ink, in anotherembodiment of at least about 10 percent by weight of the ink, and in yetanother embodiment of at least about 12 percent by weight of the ink,and in one embodiment of no more than about 32 percent by weight of theink, in another embodiment of no more than about 28 percent by weight ofthe ink, and in yet another embodiment of no more than about 25 percentby weight of the ink, although the amount can be outside of theseranges; (c) a dimer acid based tetra-amide that is the reaction productof dimer acid, ethylene diamine, and a long chain hydrocarbon havinggreater than thirty six carbon atoms and having a terminal carboxylicacid group, present in the ink in an amount in one embodiment of atleast about 10 percent by weight of the ink, in another embodiment of atleast about 13 percent by weight of the ink, and in yet anotherembodiment of at least about 16 percent by weight of the ink, and in oneembodiment of no more than about 32 percent by weight of the ink, inanother embodiment of no more than about 27 percent by weight of theink, and in yet another embodiment of no more than about 22 percent byweight of the ink, although the amount can be outside of these ranges;(d) a urethane resin derived from the reaction of two equivalents ofhydroabietyl alcohol and one equivalent of isophorone diisocyanate,present in the ink in an amount in one embodiment of at least about 6percent by weight of the ink, in another embodiment of at least about 8percent by weight of the ink, and in yet another embodiment of at leastabout 10 percent by weight of the ink, and in one embodiment of no morethan about 16 percent by weight of the ink, in another embodiment of nomore than about 14 percent by weight of the ink, and in yet anotherembodiment of no more than about 12 percent by weight of the ink,although the amount can be outside of these ranges; (e) a urethane resinthat is the adduct of three equivalents of stearyl isocyanate and aglycerol-based propoxylate alcohol, present in the ink in an amount inone embodiment of at least about 2 percent by weight of the ink, inanother embodiment of at least about 3 percent by weight of the ink, andin yet another embodiment of at least about 4.5 percent by weight of theink, and in one embodiment of no more than about 13 percent by weight ofthe ink, in another embodiment of no more than about 10 percent byweight of the ink, and in yet another embodiment of no more than about7.5 percent by weight of the ink, although the amount can be outside ofthese ranges; and (f) an antioxidant, present in the ink in an amount inone embodiment of at least about 0.01 percent by weight of the ink, inanother embodiment of at least about 0.05 percent by weight of the ink,and in yet another embodiment of at least about 0.1 percent by weight ofthe ink, and in one embodiment of no more than about 1 percent by weightof the ink, in another embodiment of no more than about 0.5 percent byweight of the ink, and in yet another embodiment of no more than about0.3 percent by weight of the ink, although the amount can be outside ofthese ranges.

The ink carrier is present in the phase change ink in any desired oreffective amount, in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 50 percent byweight of the ink, and in yet another embodiment of at least about 90percent by weight of the ink, and in one embodiment of no more thanabout 99 percent by weight of the ink, in another embodiment of no morethan about 98 percent by weight of the ink, and in yet anotherembodiment of no more than about 95 percent by weight of the ink,although the amount can be outside of these ranges.

The phase change inks contain a colorant compound of the formula

wherein R₁ is (i) a hydrogen atom, (ii) an alkyl group, (iii) an arylgroup, (iv) an arylalkyl group, or (v) an alkylaryl group, R₂ is (i) ahydrogen atom, (ii) an alkyl group, (iii) an aryl group, (iv) anarylalkyl group, (v) an alkylaryl group, or (vi) a substituent otherthan an alkyl, aryl, arylalkyl, or alkylaryl group, R₃ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, m is an integer of 0, 1, 2, 3, or 4, R₄ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, n is an integer of 0, 1, 2, 3, or 4, R₅ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, p is an integer of 0, 1, 2, 3, or 4, R₆ is (i) a directbond, (ii) an alkylene group, (iii) an arylene group, (iv) anarylalkylene group, or (v) an alkylarylene group, R₆₆ is (i) an alkylenegroup, (ii) an arylene group, (iii) an arylalkylene group, or (iv) analkylarylene group, G is (1) a hydroxy group, (2) a carboxylic acidgroup, (3) an alkyl group having at least about 8 carbon atoms, (4) anaryl group, (5) an arylalkyl group having at least about 14 carbonatoms, (6) an alkylaryl group having at least about 14 carbon atoms, (7)a group of the formula

(8) a group of the formula

(9) a group of the formula

or (10) a group of the formula

R₇ is (i) an alkyl group, (ii) an aryl group, (iii) an arylalkyl group,or (iv) an alkylaryl group, R₈ is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup, X is —O— or —NR₉—, and R₉ is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup. This colorant is present in the ink in any desired or effectiveamount to obtain the desired color or hue, in one embodiment of at leastabout 0.1 percent by weight of the ink, in another embodiment of atleast about 0.5 percent by weight of the ink, in yet another embodimentof at least about 1 percent by weight of the ink, in still anotherembodiment of at least about 2 percent by weight of the ink, and inanother embodiment of at least about 3 percent by weight of the ink, andin one embodiment of no more than about 20 percent by weight of the ink,in another embodiment of no more than about 13 percent by weight of theink, and in yet another embodiment of no more than about 6 percent byweight of the ink, although the amount can be outside of these ranges.The colorant as disclosed herein can either be the sole colorant in theink or can be present in combination with other colorants, such as dyes,pigments, mixtures thereof, and the like.

The inks can also optionally contain an antioxidant. The optionalantioxidants of the ink compositions protect the images from oxidationand also protect the ink components from oxidation during the heatingportion of the ink preparation process. Specific examples of suitableantioxidants include NAUGUARD® 524, NAUGUARD® 76, and NAUGUARD® 512(commercially available from Uniroyal Chemical Company, Oxford, Conn.),IRGANOX® 1010 (commercially available from Ciba Geigy), and the like.When present, the optional antioxidant is present in the ink in anydesired or effective amount, in one embodiment of at least about 0.01percent by weight of the ink, in another embodiment of at least about0.1 percent by weight of the ink, and in yet another embodiment of atleast about 1 percent by weight of the ink, and in one embodiment of nomore than about 20 percent by weight of the ink, in another embodimentof no more than about 5 percent by weight of the ink, and in yet anotherembodiment of no more than about 3 percent by weight of the ink,although the amount can be outside of these ranges.

The inks can also optionally contain a viscosity modifier. Examples ofsuitable viscosity modifiers include aliphatic ketones, such asstearone, and the like. When present, the optional viscosity modifier ispresent in the ink in any desired or effective amount, in one embodimentof at least about 0.1 percent by weight of the ink, in anotherembodiment of at least about 1 percent by weight of the ink, and in yetanother embodiment of at least about 10 percent by weight of the ink,and in one embodiment of no more than about 99 percent by weight of theink, in another embodiment of no more than about 30 percent by weight ofthe ink, and in yet another embodiment of no more than about 15 percentby weight of the ink, although the amount can be outside of theseranges.

Other optional additives to the inks include clarifiers, such as UNIONCAMP® X37-523-235 (commercially available from Union Camp), in an amountin one embodiment of at least about 0.01 percent by weight of the ink,in another embodiment of at least about 0.1 percent by weight of theink, and in yet another embodiment of at least about 5 percent by weightof the ink, and in one embodiment of no more than about 98 percent byweight of the ink, in another embodiment of no more than about 50percent by weight of the ink, and in yet another embodiment of no morethan about 10 percent by weight of the ink, although the amount can beoutside of these ranges, tackifiers, such as FORAL® 85, a glycerol esterof hydrogenated abietic (rosin) acid (commercially available fromHercules), FORAL® 105, a pentaerythritol ester of hydroabietic (rosin)acid (commercially available from Hercules), CELLOLYN® 21, ahydroabietic (rosin) alcohol ester of phthalic acid (commerciallyavailable from Hercules), ARAKAWA KE-311 and KE-100 Resins,triglycerides of hydrogenated abietic (rosin) acid (commerciallyavailable from Arakawa Chemical Industries, Ltd.), synthetic polyterpeneresins such as NEVTAC® 2300, NEVTAC® 100, and NEVTAC® 80 (commerciallyavailable from Neville Chemical Company), WINGTACK® 86, a modifiedsynthetic polyterpene resin (commercially available from Goodyear), andthe like, in an amount in one embodiment of at least about 0.1 percentby weight of the ink, in another embodiment of at least about 5 percentby weight of the ink, and in yet another embodiment of at least about 10percent by weight of the ink, and in one embodiment of no more thanabout 98 percent by weight of the ink, in another embodiment of no morethan about 75 percent by weight of the ink, and in yet anotherembodiment of no more than about 50 percent by weight of the ink,although the amount can be outside of these range, adhesives, such asVERSAMID® 757, 759, or 744 (commercially available from Henkel), in anamount in one embodiment of at least about 0.1 percent by weight of theink, in another embodiment of at least about 1 percent by weight of theink, and in yet another embodiment of at least about 5 percent by weightof the ink, and in one embodiment of no more than about 98 percent byweight of the ink, in another embodiment of no more than about 50percent by weight of the ink, and in yet another embodiment of no morethan about 10 percent by weight of the ink, although the amount can beoutside of these ranges, plasticizers, such as UNIPLEX® 250(commercially available from Uniplex), the phthalate ester plasticizerscommercially available from Monsanto under the trade name SANTICIZER®,such as dioctyl phthalate, diundecyl phthalate, alkylbenzyl phthalate(SANTICIZER® 278), triphenyl phosphate (commercially available fromMonsanto), KP-140®, a tributoxyethyl phosphate (commercially availablefrom FMC Corporation), MORFLEX® 150, a dicyclohexyl phthalate(commercially available from Morflex Chemical Company Inc.), trioctyltrimellitate (commercially available from Eastman Kodak Co.), and thelike, in an amount in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 1 percent byweight of the ink, and in yet another embodiment of at least about 2percent by weight of the ink, and in one embodiment of no more thanabout 50 percent by weight of the ink, in another embodiment of no morethan about 30 percent by weight of the ink, and in yet anotherembodiment of no more than about 10 percent by weight of the ink,although the amount can be outside of these ranges, and the like.

The ink compositions in one embodiment have melting points of no lowerthan about 50° C., in another embodiment of no lower than about 70° C.,and in yet another embodiment of no lower than about 80° C., and havemelting points in one embodiment of no higher than about 160° C., inanother embodiment of no higher than about 140° C., and in yet anotherembodiment of no higher than about 100° C., although the melting pointcan be outside of these ranges.

The ink compositions generally have melt viscosities at the jettingtemperature (in one embodiment no lower than about 75° C., in anotherembodiment no lower than about 100° C., and in yet another embodiment nolower than about 120° C., and in one embodiment no higher than about180° C., and in another embodiment no higher than about 150° C.,although the jetting temperature can be outside of these ranges) in oneembodiment of no more than about 30 centipoise, in another embodiment ofno more than about 20 centipoise, and in yet another embodiment of nomore than about 15 centipoise, and in one embodiment of no less thanabout 2 centipoise, in another embodiment of no less than about 5centipoise, and in yet another embodiment of no less than about 7centipoise, although the melt viscosity can be outside of these ranges.

The ink compositions can be prepared by any desired or suitable method.For example, the ink ingredients can be mixed together, followed byheating, to a temperature in one embodiment of at least about 100° C.,and in one embodiment of no more than about 140° C., although thetemperature can be outside of these ranges, and stirring until ahomogeneous ink composition is obtained, followed by cooling the ink toambient temperature (typically from about 20 to about 25° C.). The inksare solid at ambient temperature. In a specific embodiment, during theformation process, the inks in their molten state are poured into moldsand then allowed to cool and solidify to form ink sticks.

The inks can be employed in apparatus for direct printing ink jetprocesses and in indirect (offset) printing ink jet applications.Another embodiment disclosed herein is directed to a process whichcomprises incorporating an ink as disclosed herein into an ink jetprinting apparatus, melting the ink, and causing droplets of the meltedink to be ejected in an imagewise pattern onto a recording substrate. Adirect printing process is also disclosed in, for example, U.S. Pat. No.5,195,430, the disclosure of which is totally incorporated herein byreference. Yet another embodiment disclosed herein is directed to aprocess which comprises incorporating an ink as disclosed herein into anink jet printing apparatus, melting the ink, causing droplets of themelted ink to be ejected in an imagewise pattern onto an intermediatetransfer member, and transferring the ink in the imagewise pattern fromthe intermediate transfer member to a final recording substrate. In aspecific embodiment, the intermediate transfer member is heated to atemperature above that of the final recording sheet and below that ofthe melted ink in the printing apparatus. An offset or indirect printingprocess is also disclosed in, for example, U.S. Pat. No. 5,389,958, thedisclosure of which is totally incorporated herein by reference. In onespecific embodiment, the printing apparatus employs a piezoelectricprinting process wherein droplets of the ink are caused to be ejected inimagewise pattern by oscillations of piezoelectric vibrating elements.Inks as disclosed herein can also be employed in other hot melt printingprocesses, such as hot melt acoustic ink jet printing, hot melt thermalink jet printing, hot melt continuous stream or deflection ink jetprinting, and the like. Phase change inks as disclosed herein can alsobe used in printing processes other than hot melt ink jet printingprocesses.

Any suitable substrate or recording sheet can be employed, includingplain papers such as XEROX® 4024 papers, XEROX® Image Series papers,Courtland 4024 DP paper, ruled notebook paper, bond paper, silica coatedpapers such as Sharp Company silica coated paper, JuJo paper, HAMMERMILLLASERPRINT® paper, and the like, transparency materials, fabrics,textile products, plastics, polymeric films, inorganic substrates suchas metals and wood, and the like.

Specific embodiments will now be described in detail. These examples areintended to be illustrative, and the claims are not limited to thematerials, conditions, or process parameters set forth in theseembodiments. All parts and percentages are by weight unless otherwiseindicated.

EXAMPLE I

To a 500 milliliter round bottom flask with stir magnet was charged 250grams of 4-aminophenethyl alcohol (obtained from Aceto Corporation, LakeSuccess, N.Y.) and 15.6 grams of sodium carbonate (obtained from AldrichChemical Co., Milwaukee, Wis.). The mixture was heated to 140° C. in anoil bath with stirring. After the mixture was molten, 50 grams of4-bromo-1,9-N-methyl anthrapyridone (obtained from Hangsu Aolunda HighTech Industry Co. Ltd., Shanghai, China) was added and the temperatureof the oil bath was increased to 185° C. while stirring was continued.After 1 hour, the reaction mixture was quenched into 1,500 millilitersof a 0.5 percent solution of HCl in water while stirring. After severalhours, the solids were collected by vacuum filtration and washed twoadditional times in HCl/H₂O, filtering after each wash. The filtrant (abrown solution) decreased in color as each subsequent wash wasperformed. The solids were collected and dried in a vacuum oven at 60°C. The spectral strength of the product was determined using aspectrophotographic procedure based on the measurement of the product insolution by dissolving the product in toluene and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the product was measured as about 28,552 mLAbsorbance Units per gram at absorption λ_(max), 544 nanometers. Thehydroxyethyl substituted product was believed to be of the formula

EXAMPLE II

To a 1 liter flask with stir magnet was charged 50 grams of thehydroxyethyl substituted product prepared in Example I, 137.6 grams ofUNILIN 700 (a long chain fatty alcohol believed to be of the formulaCH₃(CH₂)_(n)OH wherein n represents an average number having an averagevalue of about 47 and is believed to have a range of from about 30 toabout 70, obtained from Baker Petrolite Corp., Sugarland, Tex.), 400grams of xylene (obtained from Aldrich Chemical Co.), and 2 grams ofp-toluene sulfonic acid (obtained from Aldrich Chemical Co.). The flask,equipped with a Dean-Stark trap and condenser, was placed in an oil bathat 150° C. and allowed to reflux for 4 days. The reaction product wasthen poured into a 1 liter beaker and allowed to cool and precipitate.The solids were then filtered, collected, and triturated in methanol(about 500 milliliters), followed by refiltering and repeating theprocess three times. The solids were then dried overnight in a vacuumoven at 60° C. The spectral strength of the product was determined usinga spectrophotographic procedure based on the measurement of the productin solution by dissolving the product in a 1:1 mixture oftetrahydrofuran and toluene and measuring the absorbance using a PerkinElmer Lambda 2S UV/VIS spectrophotometer. The spectral strength of theproduct was measured as about 8,921 mL Absorbance Units per gram atabsorption λ_(max), 543 nanometers. The C50 ester substituted productwas believed to be of the formula

wherein n represents an average number and has an average value of about47 and is believed to have a range of from about 30 to about 70.

EXAMPLE III

To a 125 milliliter flask with stir magnet was charged 15.1 grams of thehydroxyethyl substituted product prepared in Example I, 11.9 grams ofPRIPOL® dimer acid (a dimer diol believed to be of the formulaHOOC—C₃₆H_(64+n)—COOH wherein C₃₆H_(64+n) was a branched alkylene groupwhich may include unsaturations and cyclic groups, wherein n is aninteger of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and wherein one isomerthereof was believed to be of the formula

obtained from Uniqema, New Castle, Del.), 52.5 grams of xylene (obtainedfrom Aldrich Chemical Co.), and 0.1 grams of p-toluene sulfonic acid(obtained from Aldrich Chemical Co.). The flask, equipped with aDean-Stark trap and condenser, was placed in an oil bath at 150° C. andallowed to reflux for 4 days. The reaction product was then poured intoa 1 liter beaker and allowed to cool and precipitate. The solids werethen filtered, collected, and triturated in methanol (about 500milliliters), followed by refiltering and repeating the process threetimes. The solids were then dried overnight in a vacuum oven at 60° C.The product was believed to be of the formula

wherein C₃₆H_(64+n) was a branched alkylene group which may includeunsaturations and cyclic groups, wherein n is an integer of 0, 1, 2, 3,4, 5, 6, 7, 8, 9, or 10, and wherein one isomer thereof was believed tobe of the formula

EXAMPLE IV

To a 250 milliliter flask with stir magnet was charged 15.1 grams of thehydroxyethyl substituted product prepared in Example I, 11.4 grams ofDime Diisocyanate 1410 (a dimer diisocyanate believed to be of theformula HOOC—C₃₆H_(64+n)—COOH wherein C₃₆H_(64+n) was a branchedalkylene group which may include unsaturations and cyclic groups,wherein n is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, andwherein one isomer thereof was believed to be of the formula

obtained from Cognis Corp, Cincinnati, Ohio), 129.7 grams of xylene(obtained from Aldrich Chemical Co.), and 2 drops of FASCAT 4202catalyst (obtained from Elf Atochem North America Inc., Philadelphia,Pa.). The flask, equipped with a condenser, was placed in an oil bath at155° C. and allowed to reflux for 5 hours. An infrared spectrum of thereaction was taken to ensure that no isocyanate reactant remained andthat the reaction was complete. The reaction product was then pouredinto 1,500 milliliters of methanol and allowed to cool and precipitate.The solids were then filtered, collected, and triturated in methanol(about 500 milliliters), followed by refiltering and repeating theprocess three times. The solids were then dried overnight in a vacuumoven at 60° C. The product was believed to be of the formula

wherein C₃₆H_(64+n) was a branched alkylene group which may includeunsaturations and cyclic groups, wherein n is an integer of 0, 1, 2, 3,4, 5, 6, 7, 8, 9, or 10, and wherein one isomer thereof was believed tobe of the formula

EXAMPLE V

To a 500 milliliter round bottom flask equipped with stir magnet ischarged 275 grams of p-aminophenylacetic acid (available from TCIAmerica, Portland Oreg.) and 15.6 grams of sodium carbonate (availablefrom Aldrich Chemical Co., Milwaukee, Wis.). The mixture is heated to140° C. in an oil bath with stirring. After the mixture is molten, 50grams of 4-bromo-1,9-N-methyl anthrapyridone (available from HangsuAolunda High Tech Industry Co. Ltd., Shanghai, China) is added and thetemperature of the oil bath is increased to 185° C. while stirring iscontinued. After 1 hour, the reaction mixture is quenched into 1,500milliliters of 5 percent HCl in water while stirring. After severalhours, the solids are collected by vacuum filtration and washed twoadditional times in HCl/H₂O, filtering after each wash. The solids arecollected and dried in a vacuum oven at 60° C. It is believed that theproduct will be of the formula

EXAMPLE VI

To a 1 liter flask with stir magnet is charged 55.1 grams of thephenylacetic acid substituted product prepared in Example V, 137.6 gramsof UNICID 700 (a long chain fatty acid believed to be of the formulaCH₃(CH₂)₄₆COOH, available from Baker Petrolite Corp., Sugarland, Tex.),400 grams of xylene (available from Aldrich Chemical Co.), and 2 gramsof p-toluene sulfonic acid (available from Aldrich Chemical Co.). Theflask, equipped with a Dean-Stark trap and condenser, is placed in anoil bath at 150° C. and allowed to reflux for 4 days. The reactionproduct is then poured into a 1 liter beaker and allowed to cool andprecipitate. The solids are then filtered, collected, and triturated inmethanol (about 500 milliliters), followed by refiltering and repeatingthe process three times. The solids are then dried overnight in a vacuumoven at 60° C. It is believed that the product will be of the formula

EXAMPLE VII

To a 250 milliliter round bottom flask equipped with magnetic stir baris added 5 grams of the compound formed in Example V, 7.6 grams ofoctadecyl amine (ARMEEN 18 D, available from Akzo Nobel Chemicals Inc.,McCook, Ill.), and 70 grams of xylene. The flask is placed understirring and a condenser and Dean Stark trap in a hot oil bath at 150°C. for 48 hours. Thin layer chromatography (TLC) by normal phase in 10percent methanol in toluene is used to determine reaction completion.Thereafter, the solvent is distilled off and the product is collected.It is believed that the product will be of the formula

EXAMPLE VIII

To a 250 milliliter round bottom flask equipped with magnetic stir baris added 5 grams of the compound formed in Example V, 7.6 grams ofoctadecyl isocyanate (Mondur O, available from Bayer Corp., Pittsburgh,Pa.), 2 drops of FASCAT 4202 catalyst (available from Elf Atochem NorthAmerica Inc., Philadelphia, Pa.) and 70 grams of xylene. The flask isplaced under stirring and a condenser and Dean Stark trap in a hot oilbath at 150° C. for 5 hours. Thin layer chromatography (TLC) by normalphase in 10 percent methanol in toluene is used to determine reactioncompletion. Thereafter, the solvent is distilled off and the product iscollected. It is believed that the product will be of the formula

EXAMPLE IX

To a 250 milliliter round bottom flask in an oil bath with stir magnetis charged 10.2 grams of octadecyl amine (available from AldrichChemicals), 10.6 grams of sodium carbonate (available from AldrichChemical Co.), 150 milliliters of 2-methylpyrrolidinone (available fromAldrich Chemical Co.), 0.2 grams of copper II acetate (available fromAldrich Chemical Co.), and 33.9 grams of 4-bromo-1,9-N-methylanthrapyridone (available from Hangsu Aolunda High Tech Industry Co.Ltd., Shanghai, China), and the temperature of the oil bath is increasedto 150° C. while stirring is maintained for 16 hours. The reactionmixture is then quenched into 500 milliliters of methanol. The resultingsolid product is then filtered, collected, and triturated in methanol(about 500 milliliters), followed by refiltering and repeating theprocess three times. The solid is then dried overnight in a vacuum ovenat 60° C. It is believed that the product will be of the formula

EXAMPLE X

To a 250 milliliter round bottom flask with stir magnet is charged 13.6grams of 2-(aminophenyl)ethylamine (available from Aldrich Chemical Co.)and 150 milliliters of dry 2-methylpyrrolidinone (available from AldrichChemical Co.) under a nitrogen blanket with stirring. 29.6 grams ofoctadecylisocyanate (Mondur O, available from Bayer Corp. of Pittsburgh,Pa.) is then slowly added over 15 minutes. Normally an exotherm isobserved as the reaction of an isocyanate and aliphatic primary amine isquite exothermic. Heat is applied so as to keep the reaction mixture insolution. The reaction progress is followed by FTIR analysis as the NCOpeak (approx. 2250 cm⁻¹) disappears as the isocyanate is consumed. Themixture is then heated to 140° C. and 33.9 grams of 4-bromo-1,9-N-methylanthrapyridone (available from Hangsu Aolunda High Tech Industry Co.Ltd., Shanghai, China) and 0.2 grams of copper II acetate (availablefrom Aldrich Chemical Co.) are added and the reaction is continued for16 hours. Thereafter, the reaction mixture is quenched into 500milliliters of methanol. The resulting solid product is then filtered,collected, and triturated in methanol (about 500 milliliters), followedby refiltering and repeating the process three times. The solid is thendried overnight in a vacuum oven at 60° C. It is believed that theproduct will be of the formula

EXAMPLE XI

To a 500 milliliter round bottom flask with stir magnet was charged 10.2grams of dodecyl aniline (obtained from EMS Dottikon AG, Montvale, N.J.)and 0.3 grams of sodium carbonate (obtained from Aldrich Chemicals). Themixture was heated to 140° C. in an oil bath with stirring. After themixture was molten, 1.0 grams of 4-bromo-1,9-N-methyl anthrapyridone(obtained from Hangsu Aolunda High Tech Industry Co. Ltd., Shanghai,China) was added and the temperature of the oil bath was increased to185° C. while stirring was continued. After 1 hour, the reaction mixturewas quenched into 450 milliliters of 5 percent HCl in water. The crudeproduct, a viscous liquid, was dissolved in 250 milliliters of toluene,placed in a 1 liter separatory funnel, and washed with 450 millilitersof 5 percent HCl. The toluene layer containing the purified product wastransferred to a 1 liter round bottom flask and placed on a rotaryevaporator and the toluene was distilled off, leaving the product. Theproduct was believed to be of the formula

EXAMPLE XII

To a 500 milliliter round bottom flask with stir magnet is charged 250grams of 3-aminopropyl diethyleneglycol (DCA 163, available from DixieChemical Co., Pasadena, Tex.) and 15.6 grams of sodium carbonate(available from Aldrich Chemical Co., Milwaukee, Wis.). The mixture isheated to 140° C. in an oil bath with stirring. When the mixture ismolten, 50 grams of 4-bromo-1,9-N-methyl anthrapyridone (available fromHangsu Aolunda High Tech Industry Co. Ltd., Shanghai, China) is addedand the temperature of the oil bath is increased to 185° C. whilestirring is continued. After 1 hour, the reaction mixture is quenchedinto 1,500 milliliters of a 0.5 percent solution of HCl in water whilestirring. After several hours, the solids are collected by vacuumfiltration and washed two additional times in HCl/H₂O, filtering aftereach wash. It is believed that the product will be of the formula

EXAMPLE XIII

To a 150 milliliter round bottom flask equipped with magnetic stir baris added 5 grams of the compound formed in Example XII, 3.5 grams ofoctadecyl isocyanate (Mondur O, available from Bayer Corp., Pittsburgh,Pa.), 2 drops of FASCAT 4202 catalyst (available from Elf Atochem NorthAmerica Inc., Philadelphia, Pa.) and 70 grams of xylene. The flask isplaced under stirring and a condenser and Dean Stark trap in a hot oilbath at 150° C. for 5 hours. The solvent is distilled off and theproduct is collected. It is believed that the product will be of theformula

EXAMPLE XIV

An ink base was prepared by melting, admixing, and filtering thefollowing ingredients:

-   -   polyethylene wax (PE 655, obtained from Baker Petrolite, Tulsa,        Okla., of the formula CH₃(CH₂)₅₀CH₃), 42.01 parts by weight;    -   stearyl stearamide wax (KEMAMIDE® S-180, obtained from Crompton        Corporation, Greenwich, Conn.), 18.82 parts by weight;    -   tetra-amide resin obtained from the reaction of one equivalent        of a C-36 dimer acid obtained from Uniqema, New Castle, Del.        with two equivalents of ethylene diamine and UNICID® 700        (obtained from Baker Petrolite, Tulsa, Okla. a long chain        hydrocarbon having a terminal carboxylic acid group), prepared        as described in Example 1 of U.S. Pat. No. 6,174,937, the        disclosure of which is totally incorporated herein by reference,        24.99 parts by weight;    -   urethane resin obtained from the reaction of two equivalents of        ABITOL® E hydroabietyl alcohol (obtained from Hercules Inc.,        Wilmington, Del.) and one equivalent of isophorone diisocyanate,        prepared as described in Example 1 of U.S. Pat. No. 5,782,966,        the disclosure of which is totally incorporated herein by        reference, 8.82 parts by weight;    -   urethane resin that is the adduct of three equivalents of        stearyl isocyanate and a glycerol-based alcohol, prepared as        described in Example 4 of U.S. Pat. No. 6,309,453, the        disclosure of which is totally incorporated herein by reference,        5.21 parts by weight; and    -   NAUGUARD® 445 antioxidant (available from Uniroyal Chemical Co.,        Middlebury, Conn.), 0.15 parts by weight.        Thereafter, 566.4 grams of the ink carrier and 15.0 grams of the        colorant prepared in Example II (2.58 percent by weight) were        added to a 1 liter beaker and heated in an oven at 135° C. until        molten. Subsequently, the beaker was inserted into a heating        mantle set to 135° C. and the contents of the beaker were        stirred for 45 minutes. The resulting ink was then filtered        through a combination of Whatman # 3 and 0.2 micron NAE filters        and placed in a Mott filter assembly. Filtration was supported        by the addition of 1 percent by weight FILTER-AID, obtained from        Fluka Chemika, Switzerland, and proceeded at a temperature of        135° C. until complete after 6 hours. The dynamic viscosity of        the inks was measured using a stress-controlled Dynamic Stress        Rheometer (DSR) 2000 from Rheometric Scientific (now TA        Instruments). Geometry was 40 mm diameter Cone and Plate. A        stress of 1 Pascal was constantly maintained during a        step-stress experiment, and viscosity data points were gathered        at an approximate rate of 0.5 points per second. Each        measurement lasted approximately 5 minutes, with an        equilibration period of about 80 seconds; subsequently, data        measured between 100 and 300 seconds were averaged. The dynamic        viscosity of this ink at 140° C. was 10.80 milliPascal seconds.        The spectral strength of the ink was determined using a        spectrophotographic procedure based on the measurement of the        ink in solution by dissolving the ink in toluene and measuring        the absorbance using a Perkin Elmer Lambda 2S UV/VIS        spectrophotometer. The spectral strength of this ink was        measured as about 105 mL Absorbance Units per gram at absorption        λ_(max) of 543 nanometers.

EXAMPLE XV

The procedure of Example XIV was repeated except that the amounts of theink ingredients (weight percent) were changed as follows:

-   -   polyethylene wax: 40.77    -   stearyl stearamide: 18.27    -   tetra-amide resin: 22.64    -   first urethane resin: 8.00    -   second urethane resin: 4.72    -   antioxidant: 0.13    -   colorant: 5.47        The dynamic viscosity of this ink at 140° C. was 10.70        milliPascal seconds. The spectral strength of this ink was        measured as about 301 mL Absorbance Units per gram at absorption        λ_(max) of 543 nanometers. The ink was then cast into ink sticks        and allowed to solidify.

COMPARATIVE EXAMPLE A

The procedure of Example XIV was repeated except that an anthraquinonecolorant prepared as described in Example 2 of U.S. Pat. No. 6,395,078,the disclosure of which is totally incorporated herein by reference, wasused instead of the colorant prepared in Example II and except that theamounts of the ink ingredients (weight percent) were changed as follows:

-   -   polyethylene wax: 41.11    -   stearyl stearamide: 18.41    -   tetra-amide resin: 25.55    -   first urethane resin: 8.63    -   second urethane resin: 5.10    -   antioxidant: 0.15    -   colorant: 1.04        The ink thus prepared was cast into ink sticks and allowed to        solidify. The dynamic viscosity of this ink at 140° C. was 10.61        mPas. The spectral strength of this ink was measured as about        239 mL Absorbance Units per gram at absorption λ_(max) of 533        nanometers.

Thermal Analysis

Thermal analysis of the inks from Example XV and Comparative Example Awas carried out by means of Dynamic Mechanical Analysis (DMA) using aRSA II Solids Analyzer (obtained from Rheometric Scientific) andDifferential Scanning Calorimetry (DSC) using a DSC 2920 (obtained fromTA Instruments). Dual-cantilever DMA analysis was carried out to measuremechanical properties of the ink samples, such as modulus of elasticity(e.g. Young's Modulus, E), or loss-angle tangent (which is defined to beLoss Modulus E″, divided by Storage Modulus E′), usually as functions offrequency. The measurement can be conducted at different temperatures,which makes it a useful tool in the thermo-mechanical analysis of anink. In preparation of the measurement, the ink is cast into thin sticksor rods. Each specimen is subsequently inserted into the instrument insuch a way that the two ends of the rod rest on a fork-shaped toolconnected with a load cell, while a thin tool touches the rod in itscenter. The upper tool is moved by a special type of actuator with aconstant frequency, and the lower tool measures the response of thesolid ink material. As a result, the loss angle tangent is measured as afunction of temperature. Maxima of this curve can be associated withglass transition temperatures in many cases, and the areas under themaxima of the same curve are a relative measure of sample toughness(high values indicating high toughness). Both values are reported forthe ink samples from Example XII and Comparative Example A in the tablebelow.

DSC is a well-known method of thermal analysis, done in a special kindof calorimeter, which in case of a calibrated measurement system is ableto determine the heat capacity of a sample by comparing it with areference. If this calibration is lacking, the method is still ofsignificant analytical use, since it permits the measurement of any heateffects in the sample specimen. In the case of inks, the method can beused to determine heats of fusion (or solidification) and temperatureswhich are associated with these phase-transition processes. The typicalheat flow curve of a phase transition shows one or several maxima(peaks). The temperature of the crossover point of the baseline with theleft-flank tangent line of a peak (for heating experiments) is reportedas an “onset” temperature T_(m(onset)) of the fusing process. In thecase that such a tangent line cannot be readily determined (e.g. severalbroad, fused maxima of the curve), we have instead reported thetemperatures of the peak maxima T_(m(max)) in the table. In addition,the specific heat of fusion ΔH_(m) (in J/g) was calculated byintegration of the area under the peak. Since glass transitions manifestthemselves as step-shaped patterns in heat capacity-temperature (orheat-flow-temperature) curves, DSC offers a convenient way to determinean estimate for glass transition temperatures and intervals. In thetable, the temperature of the point of inflection of such a step-shapedcurve is reported as glass transition temperature T_(g). The resultswere as follows: Comparative Ink A Example XV Ink DSC T_(g)   8° C.  12° C. T_(m1(onset)) 76.2° C. 75.3° C. T_(m1(max)) 85.7° C. 85.2° C.T_(m2(max))  106° C.  106° C. ΔH_(m)(Jg⁻¹) 177.0 179.5 DMA T_(g)(according to tan δ)   8° C.   15° C. Area under log(tan δ)  18.3  15.6These calorimetric data indicate that the inks will exhibit very similartransfix properties. The increase in glass transition temperature isconfirmed by dual-cantilever Dynamic Mechanical Analysis. The slightlyreduced area under the log(tan δ) curve indicates a simultaneousincrease in brittleness. It is believed that this change was not causedby the colorant but by the slightly reduced content of the secondurethane resin, which can act as a toughening agent.

Print Performance: Tape Diffusion

The inks prepared in Example XV and Comparative Example A were eachincorporated into different reservoirs of the printhead of a XEROX®PHASER® 850 phase change ink jet printer and used to generate prints ofdifferent text sizes and resolutions onto HAMMERMILL LASERPRINT® paper.The resulting prints were then partially covered with SCOTCH® brandtransparent tape. Some prints were maintained at room temperature andother prints were maintained at 60° C. After 5 days, the prints wereinspected. Whereas the characters generated with the Comparative ExampleA ink and maintained at 60° C. appeared blurred, the charactersgenerated with the Example XV ink and maintained at 60° C. were clearlylegible.

To assess the result of this test in numbers, a comparative qualitativescale ranging from −3.0 to +3.0 was defined. On this scale, negativevalues indicated undesirable performance and inferiority with respect tothe reference sample (that of Comparative Example A, which by itselftherefore was rated to be ±0.0), and positive values indicated adesirable performance and hence superiority with respect to thereference sample. For the purpose of number assessment, all charactersizes and print resolutions of the text were combined. A 5-day exposureto 60° C. (accelerated test) led to a comparative subjective rating of+2.5 for the prints generated with the ink of Example XV. In comparison,the diffusion process was significantly slower at room temperature,which immediately after the end of the 5-day test led to a lowercomparative subjective rating. By estimate, this rating value waslocated between +0.5 and +1.0 for a 5-day room temperature exposure. Thesamples were then kept in storage in a dark location at room temperaturefor another 2¼ years. An inspection of the samples after this timeperiod showed that the room temperature sample of the reference wastotally blurred and illegible, whereas the sample with the ink fromExample XV appeared virtually unchanged and legible, increasing itscomparative subjective rating to a value very close to +3.0.

Print Performance: Showthrough Diffusion

One disadvantage of some magenta colorants is their relatively rapiddiffusion through paper, resulting in discoloration of the rear side ofthe paper over time. The inks prepared in Example XV and ComparativeExample A were each incorporated into different reservoirs of theprinthead of a XEROX® PHASER® 850 phase change ink jet printer and usedto generate solid fill prints onto HAMMERMILL LASERPRINT® paper. Astandard resolution of 355×464 dpi was applied. Shortly after printing,the rear sides of the printed papers were scanned with an ACSPhotometer, and the respective L*a*b* coordinates were recorded.Thereafter, some of the prints were maintained at room temperature andsome of the prints were maintained at 60° C. In defined time intervalsof approximately 1 day, 3 days, 5 days, 10 days, and 30 days as reportedin the tables, the same sites on the rear sides of the printed paperswere again scanned for their color values, and decolorations werequantified by calculating the ΔE values with respect to the initialscan. To different degrees in different parts of the visible lightspectrum, color differences with ΔE values exceeding 1.0 are perceptibleto the eye of the average observer. Low ΔE values are desirable. Theresults were as follows:

a) Room Temperature: Comparative Example A Example XV Time (Days) ΔETime (Days) ΔE 0.00 0.00 0.00 0.00 1.02 0.05 0.88 0.09 2.00 0.22 2.930.09 4.72 0.66 5.09 0.14 8.77 1.59 9.86 0.13 27.99 5.19 32.87 0.39

b) 60° C.: Comparative Example A Example XV Time (Days) ΔE Time (Days)ΔE 0.00 0.00 0.00 0.00 1.02 1.88 0.88 0.44 2.00 4.60 2.93 0.49 4.72 7.425.09 0.50 8.77 7.51 9.86 0.63 27.99 6.58 32.87 0.92The data indicate the superior performance of the ink of Example XVcompared to the ink containing the ink of Comparative Example A.Diffusion through the paper was virtually stopped. The difference becameclear after 2 days during the room temperature test and within the first24 hours during the 60° C. test.

Print Performance: Colorant Diffusion into Ink Carrier

Another disadvantage of some magenta colorants is their tendency todiffuse relatively quickly from their ink pixels into neighboring pixelson the front side of prints. This process can lead to undesirablediscoloration effects over a period of time. The inks prepared inExample XV and Comparative Example A were each incorporated intodifferent reservoirs of the printhead of a XEROX® PHASER® 850 phasechange ink jet printer. Into a third reservoir was incorporated thephase change ink carrier described in Example I. Solid fill prints weregenerated on HAMMERMILL LASERPRINT® paper with both inks by ditheringduring printing with the colorless phase change ink carrier at astandard resolution of 355×464 dpi and at 20%, 50% and 80% ink coverage.Shortly after printing, the front (printed) sides of the printed paperswere scanned with an ACS Photometer, and the respective L*a*b*coordinates were recorded. Thereafter, some of the prints weremaintained at room temperature and some of the prints were maintained at60° C. In defined time intervals of approximately 1 day, 3 days, 5 days,10 days, and 30 days as indicated in the tables, the same sites on thefront sides of the printed papers were again scanned for their colorvalues, and decolorations were quantified by calculating the ΔE valueswith respect to the initial scan. Low ΔE values are desirable. Theresults were as follows:

a) Room Temperature Comparative Example A Example XV Time (Days) ΔE Time(Days) ΔE 20% Ink Coverage 0.00 0.00 0.00 0.00 0.27 0.38 0.76 0.13 1.051.22 2.8 0.26 3.34 1.83 4.82 0.30 6.26 2.30 9.74 0.31 10.04 2.75 32.750.57 30.18 3.29 50% Ink Coverage 0.00 0.00 0.00 0.00 0.27 1.09 0.76 0.161.05 1.95 2.8 0.25 3.34 2.88 4.82 0.35 6.26 3.33 9.74 0.35 10.04 4.0832.75 0.67 30.18 4.99 80% Ink Coverage 0.00 0.00 0.00 0.00 0.27 0.800.76 0.23 1.05 1.46 2.8 0.34 3.34 2.04 4.82 0.39 6.26 1.86 9.74 0.4610.04 2.31 32.75 0.78 30.18 2.54

b) 60° C. Comparative Example A Example XV Time (Days) ΔE Time (Days) ΔE20% Ink Coverage 0.00 0.00 0.00 0.00 0.35 5.86 0.76 0.33 1.05 8.44 2.800.76 2.04 8.50 4.82 1.06 3.04 8.25 9.74 1.33 5.13 8.24 32.75 1.46 10.068.00 36.20 7.75 50% Ink Coverage 0.00 0.00 0.00 0.00 0.35 5.25 0.76 1.931.05 5.82 2.80 2.33 2.04 5.63 4.82 2.56 3.04 5.68 9.74 3.06 5.13 5.3432.75 4.38 10.06 5.39 36.20 5.40 80% Ink Coverage 0.00 0.00 0.00 0.000.35 3.30 0.76 4.09 1.05 4.46 2.80 4.88 2.04 4.42 4.82 5.32 3.04 4.399.74 6.13 5.13 4.04 32.75 8.00 10.06 3.92 36.20 3.45As the data indicate, at room temperature, the ink prepared in ExampleXV exhibited superior performance at all degrees of ink coverage. Thediffusion of dye was minimal and was equal to zero within the errorlimits of the instrument. The difference became clear after the first 24hours. At 60° C., the ink prepared in Example XV exhibited superiorperformance at 20% and 50% ink coverage, although not at 80% coverage.

Print Performance: Fingerprint Diffusion

The inks prepared in Example XV and Comparative Example A were eachincorporated into different reservoirs of the printhead of a XEROX®PHASER® 850 phase change ink jet printer and used to generate solid fillprints onto HAMMERMILL LASERPRINT® paper. Resolutions of 355×464 dpi and600×600 dpi were applied. Horizontal solid-fill stripes of different inkfill were generated, varying from 20% fill to 90% fill in 10%increments. Fingerprint diffusion tests were then carried out on theprints by having a test person rub fingers two times with fragrance-freeLUBRIDERM® hand lotion. After each rub, the fingers were dried with atowel. The surfaces of the prints were then contaminated by touchingthem with the fingers, exerting an equal and moderate pressure.Thereafter, the prints were placed into manila folders with sheets ofpaper between the samples and maintained at room temperature for fivedays, after which the prints were inspected for changes. Fingerprintsappeared quickly in the prints generated with the ink prepared inComparative Example A, but were almost not visible in the printsgenerated with the ink prepared in Example XV. To characterize thisresult in numbers, a comparative qualitative scale, ranging from −3.0 to+3.0, was established. On this scale, the reference from ComparativeExample A was assigned a value of ±0.0. Negative values representedundesirable performance and positive values represented desirableperformance superior to the reference. The prints generated with the inkof Example XV were subjectively rated +1.5 for the prints at 355×464 dpiresolution and +2.0 for the prints at 600×600 dpi resolution. Theseratings reflect the total impression, gained from all coverages between20% and 90%, for the same resolution. The samples were then stored in adark place at room temperature for 2¼ years. After this time period, thesamples were inspected again, and it was noted that the prints fromExample XV still appeared fresh and unaltered, with almost nofingerprints visible. In contrast, the reference showed a significantamount of fading dye and a speckled appearance of the surface,indicating the presence of a degrading processes.

Other embodiments and modifications may occur to those of ordinary skillin the art subsequent to a review of the information presented herein;these embodiments and modifications, as well as equivalents thereof, arealso included within the scope of this invention.

The recited order of processing elements or sequences, or the use ofnumbers, letters, or other designations therefor, is not intended tolimit a claimed process to any order except as specified in the claimitself.

1. A phase change ink composition comprising a phase change ink carrierand a colorant compound of the formula

wherein R₁ is (i) a hydrogen atom, (ii) an alkyl group, (iii) an arylgroup, (iv) an arylalkyl group, or (v) an alkylaryl group, R₂ is (i) ahydrogen atom, (ii) an alkyl group, (iii) an aryl group, (iv) anarylalkyl group, (v) an alkylaryl group, or (vi) a substituent otherthan an alkyl, aryl, arylalkyl, or alkylaryl group, R₃ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, m is an integer of 0, 1, 2, 3, or 4, R₄ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, n is an integer of 0, 1, 2, 3, or 4, R₅ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, p is an integer of 0, 1, 2, 3, or 4, R₆ is (i) a directbond, (ii) an alkylene group, (iii) an arylene group, (iv) anarylalkylene group, or (v) an alkylarylene group, R₆₆ is (i) an alkylenegroup, (ii) an arylene group, (iii) an arylalkylene group, or (iv) analkylarylene group, G is (1) a hydroxy group, (2) a carboxylic acidgroup, (3) an alkyl group having at least about 8 carbon atoms, (4) anaryl group, (5) an arylalkyl group having at least about 14 carbonatoms, (6) an alkylaryl group having at least about 14 carbon atoms, (7)a group of the formula

(8) a group of the formula

(9) a group of the formula

or (10) a group of the formula

R₇ is (i) an alkyl group, (ii) an aryl group, (iii) an arylalkyl group,or (iv) an alkylaryl group, R₈ is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup, X is —O— or —NR₉—, and R₉ is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup.
 2. An ink according to claim 1 wherein the phase change inkcarrier comprises a monoamide, a tetra-amide, or a mixture thereof. 3.An ink according to claim 1 wherein the phase change ink carriercomprises (a) stearyl stearamide, (b) a dimer acid based tetra-amidethat is the reaction product of dimer acid, ethylene diamine, andstearic acid, or (c) mixtures thereof.
 4. An ink according to claim 1wherein the phase change ink carrier comprises (a) stearyl stearamide,(b) a dimer acid based tetra-amide that is the reaction product of dimeracid, ethylene diamine, and a carboxylic acid having at least about 36carbon atoms, or (c) mixtures thereof.
 5. An ink according to claim 4wherein the carboxylic acid has at least about 40 carbon atoms, andwherein the carboxylic acid has no more than about 200 carbon atoms. 6.An ink according to claim 1 wherein the phase change ink carriercomprises an isocyanate-derived material.
 7. An ink according to claim 1wherein the phase change ink carrier comprises a urethaneisocyanate-derived material, a urea isocyanate-derived material, aurethane/urea isocyanate-derived material, or mixtures thereof.
 8. Anink according to claim 1 wherein the phase change ink carrier comprisesa mixture of one or more amides and one or more isocyanate-derivedmaterials.
 9. An ink according to claim 1 wherein the phase change inkcarrier comprises one or more materials selected from paraffins,microcrystalline waxes, polyethylene waxes, ester waxes, amide waxes,fatty acids, fatty alcohols, fatty amides, sulfonamide materials, talloil rosins, rosin esters, ethylene/vinyl acetate copolymers,ethylene/acrylic acid copolymers, ethylene/vinyl acetate/acrylic acidcopolymers, copolymers of acrylic acid with polyamides, ionomers, andmixtures thereof.
 10. An ink according to claim 1 wherein the phasechange ink carrier is present in the ink in an amount of at least about0.1 percent by weight of the ink and wherein the phase change inkcarrier is present in the ink in an amount of no more than about 99percent by weight of the ink.
 11. An ink according to claim 1 whereinthe phase change ink carrier is present in the ink in an amount of atleast about 50 percent by weight of the ink and wherein the phase changeink carrier is present in the ink in an amount of no more than about 98percent by weight of the ink.
 12. An ink according to claim 1 whereinthe phase change ink carrier is present in the ink in an amount of atleast about 90 percent by weight of the ink and wherein the phase changeink carrier is present in the ink in an amount of no more than about 95percent by weight of the ink.
 13. An ink according to claim 1 whereinthe ink carrier comprises (a) a polyethylene wax, (b) a stearylstearamide wax, (c) a dimer acid based tetra-amide that is the reactionproduct of dimer acid, ethylene diamine, and a carboxylic acid having atleast about 36 carbon atoms, (d) a urethane resin derived from thereaction of two equivalents of hydroabietyl alcohol and one equivalentof isophorone diisocyanate, (e) a urethane resin that is the adduct ofthree equivalents of stearyl isocyanate and a glycerol-based alcohol,and (f) an antioxidant.
 14. An ink according to claim 1 wherein the inkcarrier comprises (a) a polyethylene wax in an amount of at least about25 percent by weight of the ink and in an amount of no more than about60 percent by weight of the ink, (b) a stearyl stearamide wax in anamount of at least about 8 percent by weight of the ink and in an amountof no more than about 32 percent by weight of the ink, (c) a dimer acidbased tetra-amide that is the reaction product of dimer acid, ethylenediamine, and a carboxylic acid having at least about 36 carbon atoms inan amount of at least about 10 percent by weight of the ink and in anamount of no more than about 32 percent by weight of the ink, (d) aurethane resin derived from the reaction of two equivalents ofhydroabietyl alcohol and one equivalent of isophorone diisocyanate in anamount of at least about 6 percent by weight of the ink and in an amountof no more than about 16 percent by weight of the ink, (e) a urethaneresin that is the adduct of three equivalents of stearyl isocyanate anda glycerol-based alcohol in an amount of at least about 2 percent byweight of the ink and in an amount of no more than about 13 percent byweight of the ink, and (f) an antioxidant in an amount of at least about0.01 percent by weight of the ink and in an amount of no more than about1 percent by weight of the ink.
 15. An ink according to claim 1 whereinthe colorant is present in the ink in an amount of at least about 0.1percent by weight of the ink.
 16. An ink according to claim 1 whereinthe colorant is present in the ink in an amount of at least about 1percent by weight of the ink.
 17. An ink according to claim 1 whereinthe colorant is present in the ink in an amount of at least about 3percent by weight of the ink.
 18. An ink according to claim 1 whereinthe colorant is present in the ink in an amount of no more than about 20percent by weight of the ink.
 19. An ink according to claim 1 whereinthe colorant is present in the ink in an amount of no more than about 13percent by weight of the ink.
 20. An ink according to claim 1 whereinthe colorant is present in the ink in an amount of no more than about 6percent by weight of the ink.
 21. An ink according to claim 1 whereinthe ink has a melting point of no lower than about 50° C. and whereinthe ink has a melting point of no higher than about 160° C.
 22. An inkaccording to claim 1 wherein the ink has a melting point of no lowerthan about 70° C. and wherein the ink has a melting point of no higherthan about 140° C.
 23. An ink according to claim 1 wherein the ink has amelting point of no lower than about 80° C. and wherein the ink has amelting point of no higher than about 100° C.
 24. An ink according toclaim 1 wherein the ink has a melt viscosity at a temperature of about140° C. of no more than about 30 centipoise.
 25. An ink according toclaim 1 wherein the ink has a melt viscosity at a temperature of about140° C. of no more than about 20 centipoise.
 26. An ink according toclaim 1 wherein the ink has a melt viscosity at a temperature of about140° C. of no more than about 15 centipoise.
 27. An ink according toclaim 1 wherein the ink has a melt viscosity at a temperature of about140° C. of no less than about 2 centipoise.
 28. An ink according toclaim 1 wherein the ink has a melt viscosity at a temperature of about140° C. of no less than about 5 centipoise.
 29. An ink according toclaim 1 wherein the ink has a melt viscosity at a temperature of about140° C. of no less than about 7 centipoise.
 30. A process whichcomprises (1) incorporating into an ink jet printing apparatus a phasechange ink composition comprising a phase change ink carrier and acolorant compound of the formula

wherein R₁ is (i) a hydrogen atom, (ii) an alkyl group, (iii) an arylgroup, (iv) an arylalkyl group, or (v) an alkylaryl group, R₂ is (i) ahydrogen atom, (ii) an alkyl group, (iii) an aryl group, (iv) anarylalkyl group, (v) an alkylaryl group, or (vi) a substituent otherthan an alkyl, aryl, arylalkyl, or alkylaryl group, R₃ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, m is an integer of 0, 1, 2, 3, or 4, R₄ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, n is an integer of 0, 1, 2, 3, or 4, R₅ is (i) an alkylgroup, (ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylarylgroup, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, p is an integer of 0, 1, 2, 3, or 4, R₆ is (i) a directbond, (ii) an alkylene group, (iii) an arylene group, (iv) anarylalkylene group, or (v) an alkylarylene group, R₆₆ is (i) an alkylenegroup, (ii) an arylene group, (iii) an arylalkylene group, or (iv) analkylarylene group, G is (1) a hydroxy group, (2) a carboxylic acidgroup, (3) an alkyl group having at least about 8 carbon atoms, (4) anaryl group, (5) an arylalkyl group having at least about 14 carbonatoms, (6) an alkylaryl group having at least about 14 carbon atoms, (7)a group of the formula

(8) a group of the formula

(9) a group of the formula

or (10) a group of the formula

R₇ is (i) an alkyl group, (ii) an aryl group, (iii) an arylalkyl group,or (iv) an alkylaryl group, R₈ is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup, X is —O— or —NR₉—, and R₉ is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup; (2) melting the ink; and (3) causing droplets of the melted inkto be ejected in an imagewise pattern onto a substrate.
 31. A processaccording to claim 30 wherein the printing apparatus employs apiezoelectric printing process wherein droplets of the ink are caused tobe ejected in imagewise pattern by oscillations of piezoelectricvibrating elements.
 32. A process according to claim 30 wherein thesubstrate is a final recording sheet and droplets of the melted ink areejected in an imagewise pattern directly onto the final recording sheet.33. A process according to claim 30 wherein the substrate is anintermediate transfer member and droplets of the melted ink are ejectedin an imagewise pattern onto the intermediate transfer member followedby transfer of the imagewise pattern from the intermediate transfermember to a final recording sheet.
 34. A process according to claim 33wherein the intermediate transfer member is heated to a temperatureabove that of the final recording sheet and below that of the melted inkin the printing apparatus.
 35. An ink according to claim 1 wherein thecolorant compound is of the formula


36. An ink according to claim 35 wherein R₁ is a methyl group, R₂ is ahydrogen atom, m, n, and p are all 0, R₆ is —CH₂— or —CH₂CH₂—, and G isa group of the formula

a group of the formula

a group of the formula

or a group of the formula


37. An ink according to claim 35 wherein R₆ is a direct bond.
 38. An inkaccording to claim 35 wherein R₆ is an alkylene group, an arylene group,an arylalkylene group, or an alkylarylene group.
 39. An ink according toclaim 1 wherein the colorant compound is of the formula


40. An ink according to claim 1 wherein G is a hydroxy group.
 41. An inkaccording to claim 1 wherein G is a carboxylic acid group.
 42. An inkaccording to claim 1 wherein G is an alkyl group having at least about 8carbon atoms.
 43. An ink according to claim 1 wherein G is an alkylgroup having at least about 18 carbon atoms.
 44. An ink according toclaim 1 wherein G is a linear alkyl group.
 45. An ink according to claim1 wherein G is a substituted alkyl group.
 46. An ink according to claim1 wherein G is an unsubstituted alkyl group.
 47. An ink according toclaim 1 wherein G is an alkyl group wherein hetero atoms selected fromoxygen, nitrogen, sulfur, silicon, phosphorus, or mixtures thereof arepresent in the alkyl group.
 48. An ink according to claim 1 wherein G isan alkyl group wherein no hetero atoms are present in the alkyl group.49. An ink according to claim 1 wherein G is an arylalkyl group havingat least about 14 carbon atoms.
 50. An ink according to claim 1 whereinG is an arylalkyl group having at least about 24 carbon atoms.
 51. Anink according to claim 1 wherein G is an arylalkyl group wherein thealkyl portion thereof has at least about 8 carbon atoms.
 52. An inkaccording to claim 1 wherein G is an arylalkyl group wherein the alkylportion thereof has at least about 18 carbon atoms.
 53. An ink accordingto claim 1 wherein G is a substituted arylalkyl group.
 54. An inkaccording to claim 1 wherein G is an unsubstituted arylalkyl group. 55.An ink according to claim 1 wherein G is an arylalkyl group whereinhetero atoms selected from oxygen, nitrogen, sulfur, silicon,phosphorus, or mixtures thereof are present in the arylalkyl group. 56.An ink according to claim 1 wherein G is an arylalkyl group wherein nohetero atoms are present in the arylalkyl group.
 57. An ink according toclaim 1 wherein G is an alkylaryl group having at least about 14 carbonatoms.
 58. An ink according to claim 1 wherein G is an alkylaryl grouphaving at least about 24 carbon atoms.
 59. An ink according to claim 1wherein G is an alkylaryl group wherein the alkyl portion thereof has atleast about 8 carbon atoms.
 60. An ink according to claim 1 wherein G isan alkylaryl group wherein the alkyl portion thereof has at least about18 carbon atoms.
 61. An ink according to claim 1 wherein G is asubstituted alkylaryl group.
 62. An ink according to claim 1 wherein Gis an unsubstituted alkylaryl group.
 63. An ink according to claim 1wherein G is an alkylaryl group wherein hetero atoms selected fromoxygen, nitrogen, sulfur, silicon, phosphorus, or mixtures thereof arepresent in the alkylaryl group.
 64. An ink according to claim 1 whereinG is an alkylaryl group wherein no hetero atoms are present in thealkylaryl group.
 65. An ink according to claim 1 wherein G is a group ofthe formula


66. An ink according to claim 65 wherein R₇ is an alkyl group.
 67. Anink according to claim 66 wherein the alkyl group has at least about 8carbon atoms.
 68. An ink according to claim 66 wherein the alkyl grouphas at least about 18 carbon atoms.
 69. An ink according to claim 66wherein the alkyl group is a linear alkyl group.
 70. An ink according toclaim 66 wherein the alkyl group is a substituted alkyl group.
 71. Anink according to claim 66 wherein the alkyl group is an unsubstitutedalkyl group.
 72. An ink according to claim 66 wherein the alkyl group isan alkyl group wherein hetero atoms selected from oxygen, nitrogen,sulfur, silicon, phosphorus, or mixtures thereof are present in thealkyl group.
 73. An ink according to claim 66 wherein the alkyl group isan alkyl group wherein no hetero atoms are present in the alkyl group.74. An ink according to claim 65 wherein R₇ is an arylalkyl group. 75.An ink according to claim 74 wherein the arylalkyl group has at leastabout 14 carbon atoms.
 76. An ink according to claim 74 wherein thearylalkyl group has at least about 24 carbon atoms.
 77. An ink accordingto claim 74 wherein the alkyl portion of the arylalkyl group has atleast about 8 carbon atoms.
 78. An ink according to claim 74 wherein thealkyl portion of the arylalkyl group has at least about 18 carbon atoms.79. An ink according to claim 74 wherein the arylalkyl group is asubstituted arylalkyl group.
 80. An ink according to claim 74 whereinthe arylalkyl group is an unsubstituted arylalkyl group.
 81. An inkaccording to claim 74 wherein the arylalkyl group is an arylalkyl groupwherein hetero atoms selected from oxygen, nitrogen, sulfur, silicon,phosphorus, or mixtures thereof are present in the arylalkyl group. 82.An ink according to claim 74 wherein the arylalkyl group is an arylalkylgroup wherein no hetero atoms are present in the arylalkyl group.
 83. Anink according to claim 65 wherein R₇ is an alkylaryl group.
 84. An inkaccording to claim 83 wherein the alkylaryl group has at least about 14carbon atoms.
 85. An ink according to claim 83 wherein the alkylarylgroup has at least about 24 carbon atoms.
 86. An ink according to claim83 wherein the alkyl portion of the alkylaryl group has at least about 8carbon atoms.
 87. An ink according to claim 83 wherein the alkyl portionof the alkylaryl group has at least about 18 carbon atoms.
 88. An inkaccording to claim 83 wherein the alkylaryl group is a substitutedalkylaryl group.
 89. An ink according to claim 83 wherein the alkylarylgroup is an unsubstituted alkylaryl group.
 90. An ink according to claim83 wherein the alkylaryl group is an alkylaryl group wherein heteroatoms selected from oxygen, nitrogen, sulfur, silicon, phosphorus, ormixtures thereof are present in the alkylaryl group.
 91. An inkaccording to claim 83 wherein the alkylaryl group is an alkylaryl groupwherein no hetero atoms are present in the alkylaryl group.
 92. An inkaccording to claim 65 wherein R₇ is an aryl group.
 93. An ink accordingto claim 1 wherein G is a group of the formula—(C_(a)H_(2a)O)bR₁₀or—(OC_(a)H_(2a))bOR₁₀ wherein a is an integer representing the number ofcarbon atoms, b is an integer representing the number of repeat units,and R₁₀ is a hydrogen atom, an alkyl group, an aryl group, an arylalkylgroup, or an alkylaryl group.
 94. An ink according to claim 1 wherein Gis a group of the formula


95. An ink according to claim 1 wherein G is a group of the formula


96. An ink according to claim 1 wherein G is a group of the formula


97. An ink according to claim 1 wherein G is a group of the formula

wherein X is —O—.
 98. An ink according to claim 1 wherein G is a groupof the formula

wherein X is —NR₉—.
 99. An ink according to claim 1 wherein the totalnumber of carbon atoms in R₁+R₂+R₃+R₄+R₅+(R₆ or R₆₆)+R₇+R₈+R₉ is no morethan about
 200. 100. An ink according to claim 1 wherein the totalnumber of carbon atoms in R₁+R₂+R₃+R₄+R₅+(R₆ or R₆₆)+R₇+R₈+R₉ is no morethan about
 100. 101. An ink according to claim 1 wherein the totalnumber of carbon atoms in R₁+R₂+R₃+R₄+R₅+(R₆ or R₆₆)+R₇+R₈+R₉ is atleast about
 12. 102. An ink according to claim 1 wherein the totalnumber of carbon atoms in R₁+R₂+R₃+R₄+R₅+(R₆ or R₆₆)+R₇+R₈+R₉ is atleast about
 24. 103. An ink according to claim 1 wherein the totalnumber of carbon atoms in R₁+R₂+R₃+R₄+R₅+(R₆ or R₆₆)+R₇+R₈+R₉ is atleast about
 36. 104. An ink according to claim 1 wherein the totalnumber of carbon atoms in R₁+R₂+R₃+R₄+R₅+(R₆ or R₆₆)+R₇+R₈+R₉ is atleast about
 48. 105. An ink according to claim 1 wherein the colorant isof the formula


106. An ink according to claim 1 wherein the colorant is of the formula

wherein n represents an average number and has an average value of about47.
 107. An ink according to claim 1 wherein the colorant is of theformula


108. An ink according to claim 1 wherein the colorant is of the formula


109. An ink according to claim 1 wherein the colorant is of the formula


110. An ink according to claim 1 wherein the colorant is of the formula


111. An ink according to claim 1 wherein the colorant is of the formula


112. An ink according to claim 1 wherein the colorant is of the formula


113. An ink according to claim 1 wherein the colorant is of the formula


114. A phase change ink composition comprising a phase change inkcarrier and a colorant compound which is a dimeric material comprisingtwo moieties of the formula or

wherein each R₁, independently of the other, is (i) a hydrogen atom,(ii) an alkyl group, (iii) an aryl group, (iv) an arylalkyl group, or(v) an alkylaryl group, each R₂, independently of the other, is (i) ahydrogen atom, (ii) an alkyl group, (iii) an aryl group, (iv) anarylalkyl group, (v) an alkylaryl group, or (vi) a substituent otherthan an alkyl, aryl, arylalkyl, or alkylaryl group, each R₃,independently of the other, is (i) an alkyl group, (ii) an aryl group,(iii) an arylalkyl group, (iv) an alkylaryl group, or (v) a substituentother than an alkyl, aryl, arylalkyl, or alkylaryl group, each m,independently of the other, is an integer of 0, 1, 2, 3, or 4, each R₄,independently of the other, is (i) an alkyl group, (ii) an aryl group,(iii) an arylalkyl group, (iv) an alkylaryl group, or (v) a substituentother than an alkyl, aryl, arylalkyl, or alkylaryl group, each n,independently of the other, is an integer of 0, 1, 2, 3, or 4, each R₅,independently of the other, is (i) an alkyl group, (ii) an aryl group,(iii) an arylalkyl group, (iv) an alkylaryl group, or (v) a substituentother than an alkyl, aryl, arylalkyl, or alkylaryl group, each p,independently of the other, is an integer of 0, 1, 2, 3, or 4, each R₆,independently of the other, is (i) a direct bond, (ii) an alkylenegroup, (iii) an arylene group, (iv) an arylalkylene group, or (v) analkylarylene group, each R₆₆, independently of the other, is (i) analkylene group, (ii) an arylene group, (iii) an arylalkylene group, or(iv) an alkylarylene group, each G, independently of the other, is (1)an alkylene group, (2) an arylene group, (3) an arylalkylene group, (4)an alkylarylene group, (5) a group of the formula

(6) a group of the formula

(7) a group of the formula

or (8) a group of the formula

each R₇, independently of the other, is (i) an alkylene group, (ii) anarylene group, (iii) an arylalkylene group, or (iv) an alkylarylenegroup, each R₈, independently of the other, is (i) a hydrogen atom, (ii)an alkyl group, (iii) an aryl group, (iv) an arylalkyl group, or (v) analkylaryl group, each X, independently of the other, is —O— or —NR₉—,and each R₉, independently of the other, is (i) a hydrogen atom, (ii) analkyl group.
 115. An ink according to claim 114 wherein the colorant isof the formula

wherein R represents an alkyl, aryl, arylalkyl, or alkylaryl grouphaving no substituents thereon and no hetero atoms therein,

wherein R represents an alkyl, aryl, arylalkyl, or alkylaryl group asdefined hereinabove having no substituents thereon and no hetero atomstherein, or mixtures thereof.
 116. An ink according to claim 114 whereinthe colorant is of the formula

wherein C₃₆H_(64+n) is a branched alkylene group which may includeunsaturations and cyclic groups, wherein n is an integer of 0, 1, 2, 3,4, 5, 6, 7, 8, 9, or
 10. 117. An ink according to claim 114 wherein thecolorant is of the formula


118. An ink according to claim 114 wherein the colorant is of theformula

wherein C₃₆H_(64+n) is a branched alkylene group which may includeunsaturations and cyclic groups, wherein n is an integer of 0, 1, 2, 3,4, 5, 6, 7, 8, 9, or
 10. 119. An ink according to claim 114 wherein thecolorant is of the formula


120. A phase change ink composition comprising a phase change inkcarrier and a colorant compound comprising three or more moieties of theformula

wherein each R₁, independently of the other, is (i) a hydrogen atom,(ii) an alkyl group, (iii) an aryl group, (iv) an arylalkyl group, or(v) an alkylaryl group, each R₂, independently of the other, is (i) ahydrogen atom, (ii) an alkyl group, (iii) an aryl group, (iv) anarylalkyl group, (v) an alkylaryl group, or (vi) a substituent otherthan an alkyl, aryl, arylalkyl, or alkylaryl group, each R₃,independently of the other, is (i) an alkyl group, (ii) an aryl group,(iii) an arylalkyl group, (iv) an alkylaryl group, or (v) a substituentother than an alkyl, aryl, arylalkyl, or alkylaryl group, each m,independently of the other, is an integer of 0, 1, 2, 3, or 4, each R₄,independently of the other, is (i) an alkyl group, (ii) an aryl group,(iii) an arylalkyl group, (iv) an alkylaryl group, or (v) a substituentother than an alkyl, aryl, arylalkyl, or alkylaryl group, each n,independently of the other, is an integer of 0, 1, 2, 3, or 4, each R₅,independently of the other, is (i) an alkyl group, (ii) an aryl group,(iii) an arylalkyl group, (iv) an alkylaryl group, or (v) a substituentother than an alkyl, aryl, arylalkyl, or alkylaryl group, each p,independently of the other, is an integer of 0, 1, 2, 3, or 4, each R₆,independently of the other, is (i) a direct bond, (ii) an alkylenegroup, (iii) an arylene group, (iv) an arylalkylene group, or (v) analkylarylene group, each R₆₆, independently of the other, is (i) analkylene group, (ii) an arylene group, (iii) an arylalkylene group, or(iv) an alkylarylene group, each G, independently of the other, is (1)an alkylene group, (2) an arylene group, (3) an arylalkylene group, (4)an alkylarylene group, (5) a group of the formula

(6) a group of the formula

(7) a group of the formula

or (8) a group of the formula

each R₇, independently of the other, is (i) an alkylene group, (ii) anarylene group, (iii) an arylalkylene group, or (iv) an alkylarylenegroup, each R₈, independently of the other, is (i) a hydrogen atom, (ii)an alkyl group, (iii) an aryl group, (iv) an arylalkyl group, or (v) analkylaryl group, each X, independently of the other, is —O— or —NR₉—,and each R₉, independently of the other, is (i) a hydrogen atom, (ii) analkyl group.